Trends in the usage of bidentate phosphines as ligands in nickel catalysis of hydrogenation reactions

A critically important process in catalysis is the formation of an active catalyst from the combination of a metal precursor and a ligand, as the efficacy of this reaction governs the amount of active catalyst. This review is a compacted but comprehensive review of reactions catalyzed by nickel and an added bidentate phosphine, specifically in regards to cross-coupling reactions, a large enough sample pool to still elucidate information over this catalytic process. The highlight in the review is the steps of transformation and the combination of precatalyst and ligand into an active catalyst and the potential effects of this transformation on nickel catalysis. Overall the most widely used nickel precatalyst with free bidentate phosphines is Ni(cod)2, followed by Ni(acac)2 and Ni(OAc)2. By compiling the reports surveyed, we have calculated statistics of the usage and efficacy of each ligand with Ni(cod)2 and other nickel sources. The most common bidentate phosphines are simple, relatively inexpensive ligands, such as DPPE, DCPE, DPPP, and DPPB, along with more complex backbones, such as DPPF and Xantphos. The use of expensive chiral phosphines is more scattered, but the most common ligands include BINAP, Me-Duphos, Josiphos, and related analogs. Covering this range of ligands is to not only screen the efficacy of the ligands themselves, but push the worthwhile efficacy in nickel catalysis itself, as an option for a far more affordable and accessible catalytic approach than some of the most currently popular alternatives. This thesis is an excerpt of the complete published review, in order to concisely show the analysis of trends. Specifically, it investigates hydrogenation, due to its place as a kind of median between commonality and interesting results in the review as a whole.

TRENDS IN THE USAGE OF BIDENTATE PHOSPHINES AS LIGANDS IN NICKEL CATALYSIS OF HYDROGENATION REACTIONS by Justis Aderibigbe A Senior Honor Thesis Submitted to the Faculty of The University of Utah In Partial Fulfillment of the Requirements for the Honors Degree in Bachelor of Science In Chemistry Approved: ______________________________ Thesis Faculty Supervisor _____________________________ Chair, Department of Chemistry ____________________________ Honors Faculty Advisor ____________________________ Sylvia D. Torti, PhD Dean, Honors College July 2021 Copyright © 2021 All Rights Reserved ABSTRACT A critically important process in catalysis is the formation of an active catalyst from the combination of a metal precursor and a ligand, as the efficacy of this reaction governs the amount of active catalyst. This review is a compacted but comprehensive review of reactions catalyzed by nickel and an added bidentate phosphine, specifically in regards to cross-coupling reactions, a large enough sample pool to still elucidate information over this catalytic process. The highlight in the review is the steps of transformation and the combination of precatalyst and ligand into an active catalyst and the potential effects of this transformation on nickel catalysis. Overall the most widely used nickel precatalyst with free bidentate phosphines is Ni(cod)2, followed by Ni(acac)2 and Ni(OAc)2. By compiling the reports surveyed, we have calculated statistics of the usage and efficacy of each ligand with Ni(cod)2 and other nickel sources. The most common bidentate phosphines are simple, relatively inexpensive ligands, such as DPPE, DCPE, DPPP, and DPPB, along with more complex backbones, such as DPPF and Xantphos. The use of expensive chiral phosphines is more scattered, but the most common ligands include BINAP, Me-Duphos, Josiphos, and related analogs. Covering this range of ligands is to not only screen the efficacy of the ligands themselves, but push the worthwhile efficacy in nickel catalysis itself, as an option for a far more affordable and accessible catalytic approach than some of the most currently popular alternatives. This thesis is an excerpt of the complete published review, in order to concisely show the analysis of trends. Specifically, it investigates hydrogenation, due to its place as a kind of median between commonality and interesting results in the review as a whole. ii TABLE OF CONTENTS ABSTRACT ii INTRODUCTION 1 BACKGROUND 5 SCOPE 6 LITERATURE REVIEW 10 CONCLUSION 22 REFERENCES 27 iii 1 1.Introduction Research into transition metal-catalyzed transformations in organic chemistry has quickly expanded to become a popular topic of study for chemists over the last half-century. It is nearly impossible to think of a reaction series that does not utilize a transition metalcatalyzed route to make traditionally difficult carbon−carbon bonds, induce and control chirality, or control redox processes. Primary to this exploration has been the reaction chemistry of precious metals in the platinum group, such as rhodium,1−3 iridium,4 ruthenium,5−8 platinum,9−11 and, in particular, palladium.12−23 The prevalence of these metals in organic chemistry stems from their predictable two-electron transformations and stability under a variety of conditions. The high specific activities and relative stabilities of these metals and their organometallic complexes has resulted in utilization of catalysts based on noble metals being deployed on an industrial scale with highly specialized catalysts for nearly every synthesis based chemical industry.24−26 Nobel Prizes in Chemistry were awarded in 2005 and 2010 to recognize the impact that transition-metal catalysis has had on the field. While precious metals are undeniably useful and practical, they are also expensive and among the rarest of all elements found in the earth’s crust.27 The rarity of these metals, along with some limits on their reactivity, has resulted in researchers pursuing alternative methods with other metals capable of the same transformations at a lower cost. In parallel, these studies have also focused on overcoming some of the limitations of palladium and other workhorse metals. 2 One well-studied alternative for precious metals is nickel. Nickel is much less expensive than palladium or platinum on a per mole basis, and it has shown both analogous and complementary reactivity to precious metals. However, nickel is considerably more oxophilic than palladium,28−30 which limits its functional group tolerance. However, this oxophilicity leads to oxidative addition reactions of normally stable substrates, such as aryl esters31,32 and aryl ethers.33−37 Nickel also possesses defined one-electron redox potentials, which can provide for a variety of oxidation states, leading to less defined reaction pathways and outcomes. The differential reactivity imposed by the stability of variable oxidation states typically results in less-than-ideal mechanistic understanding, particularly in off pathway reactions, which can result in higher catalyst loading. While the activities of workhorse transition metals result from the atomic properties of the metals, fine-tuning of the reactivity of these properties is dependent on the ligands employed. Understanding of this metal−ligand interaction and the resulting reactivity trends continues to be a large field of study for many metals. 1.1. General Introduction to Bidentate Phosphines: Phosphines are one of the most common ligand classes with all transition metals. Their ability to bind strongly to metals, relative ease of preparation, and easy tuning of both steric and electronic properties have led to wide-ranging studies were researchers design metal-catalyzed reactions with precision based on the steric and electronic properties of the phosphine ligand. Monodentate phosphines, the most straightforward phosphine class, are very common and have an easily predictable individual binding with the metal because only two modes exist: bound and not bound. 3 In a steric sense, the bound ligand limits the binding pocket of a substrate, thus defining the directionality of the substrate−metal interaction. This binding pocket specifies the size of a substrate that can interact with the metal. In an electronic sense, the electron donacity of a ligand influences the properties of the metal center, such as nucleophilicity and redox capability. As useful as monodentate phosphines are, many situations exist where they are not an ideal choice. For instance, because of the dynamic bonding of metals and phosphines, the metal to ligand ratios are not always known or easily controlled, which can result in off-pathway reactions lowering yields and selectivity’s. Asymmetric catalysis can also be more challenging to achieve with monodentate chiral phosphines (or related organophosphorus ligands) because of insufficient influence on the orientation of the substrate,38,39 although phosphine derivatives, such as phosphoramidites, have been designed to enhance the asymmetric effect of the monodentate ligand.40−43 4 Also, side reactions, such as β-hydride elimination are more likely to occur with monodentate phosphines as ligands because of their propensity to dissociate and leave an open coordination site.44−46 Bidentate phosphines have been well-studied in parallel with monodentate phosphines to give a potential solution to these problems. Tethering the phosphines together with a backbone increases the likelihood that both will be bound to the metal center, which closes a potentially open coordination site and also helps to define a specific binding pocket for asymmetric catalysis. Beyond the electronic and steric modification of the phosphine substituents, the backbone of the bidentate phosphine can also be electronically and sterically modified (Figure 1). Control of the backbone structure, in particular, can have powerful implications for catalysis via the differential bite angle. The work of von Leeuwen and co-workers47 demonstrates the effect of varying bite angle in a catalytic reaction. The researchers studied a Ni-catalyzed hydrocyanation of terminal alkenes in which the bite angle of the bidentate phosphine proved to be crucial for product formation.47 When the bite angle of the phosphine is ∼90°, the phosphine stabilizes a square planar LNi(CN)2 species, which is a catalyst sink. An increase in the bite angle of the phosphine leads to destabilization of the square planar complex, which in turn results in increased stabilization of tetrahedral Ni(0) complexes. The Ni(0) complex occurs after the product-forming reductive elimination step. In sum, use of a bidentate phosphine with a bite angle of >100° results in destabilization of intermediates and stabilization of products, leading to increased reactivity.47,48 The wide 5 array of potential modifications of bidentate phosphines results in ligands ranging from small phosphines with aliphatic backbones (such as 1,2-bis(diphenylphosphino)ethane (DPPE)) to large phosphines with much more sterically hindered and electronically diverse backbones (such as (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (Xantphos)). With imagination and organic synthesis skills, any bidentate phosphine can be tuned to deliver the precise electronic and steric properties necessary for a given reaction. While phosphines are common ligands, they are not always perfect spectators to the reactions occurring at the metal center. Previous research has shown that C−P ligands can undergo oxidative addition under certain conditions, namely, electron rich substrates and sterically hindered bidentate phosphines.49 While rare, this phenomenon should undoubtedly be taken into account when performing a catalytic reaction. 2. Background of the Nickel precatalyst Many common nickel precatalysts exist in a Ni(II) oxidation state, as these complexes are air-stable, inexpensive, and easy to use, but most reactions employ Ni(0) catalysts, which can either perform oxidative addition or oxidative coupling. As a result, Ni(II) precatalysts often must be reduced with an exogenous reductant or a reducing substrate to Ni(0) to become catalytically active. This extra step is not very well understood and can result in catalyst death if it does not occur efficiently. For instance, nickel can also perform several chemical transformations in a Ni(I)−Ni(III) redox cycle or in single- 6 electron conversions from Ni(I).50−54 To avoid the extra reduction step, many chemists use prereduced Ni(0) . The advantages of these complexes are that they incorporate catalytically active nickel directly into the reaction, thus negating any potential problems with in situ reductions and facilitating rapid ligand screens of catalytic reactions. The disadvantages are that these complexes are comparatively expensive ($9625/mol for Ni(cod)2 vs ∼$1800/mol for bis(acetylacetonate)nickel (Ni(acac)2) and ∼$500/mol for NiCl2·6H2O)55 and are typically air- and heat-sensitive, requiring storage in a freezer in a glovebox filled with inert gas. Also, COD can bind to the Ni center strongly enough to be a detriment to catalysis.56,57 Currently, momentum exists in the field to move away from expensive and unstable Ni(0) complexes to cheaper air-stable Ni(II) compounds, and scientists have reported a considerable amount of effort toward their utilization, but Ni(cod)2 is still the nickel source of choice. A comparison with prices of Pd sources shows that PdCl2 (at $9822/mol) is similarly priced to Ni(cod)2, and Pd(OAc)2, at $20137/mol,55 is significantly more expensive. However, counterbalancing this expense is the ability to use much lower catalyst loadings with Pd relative to Ni. As a result, one of the main points of this Review is to attempt to identify mixtures of nickel precatalysts and ligands which form catalytically active species. Achieving a desired catalytically active nickel complex provides for a reduction in the amount of Ni required for a given reaction, which could increase its competitiveness with Pd. 7 3. Scope To our knowledge, no reviews have focused explicitly on structure−activity relationships in catalyst formation of reactions catalyzed by bidentate phosphines and nickel. The lack of understanding indicates that a review is warranted to determine trends governed by the formation of an active catalyst. Many reviews cover nickel-catalyzed reactions, but these generally focus on one reaction class and examine a wide variety of ligands.29,39,83−91 In contrast, our analysis focuses on the subsets of reactions that use Ni and bidentate phosphines as ligands to produce products through the end of 2018. The point of this study is to examine the yields and conversions of each reaction and look for trends existing between different ligand/ precatalyst combinations and lower or higher yields. We hypothesize that ligands which form (phosphine)2Ni, such as DPPE and DPPP, will be less effective in catalysis, and that ligands which do not form (phosphine)2Ni, such as DPPF, DPEPhos, and DPPB, will be more effective in catalysis. Throughout this Review, we offer commentary and point out when a given reaction either confirms or disproves this hypothesis. Where appropriate, analysis is also provided on reaction mechanisms and different ligand/precatalyst combinations. Our Review is split into sections that focus on catalytic reactions and only mention critical stoichiometric reactions applying directly to the analysis of a given catalytic transformation. We have divided the Review by general reaction class, followed by specific reactions. Where many examples of a particular reaction exist, we have further 8 subdivided the sections by the initial oxidation state of the nickel precatalyst and analyzed the yield in a reaction of each nickel source ligand by ligand for a deep and thorough examination of the effectiveness of each nickel source with bidentate phosphines. In the end, we conclude with an overall survey of nickel sources and focus on Ni(cod)2, which is by far the most common Ni source. Equations, schemes, and tables visualize these data, along with radial charts, which give a visual representation of the relative efficacy of a nickel precatalyst and ligand in a given reaction. Radial maps are organized by the number of examples of each combination of Ni source and ligand, separated by the overall yield of each reaction. The yields are split into four categories: low (0−25% yield), moderately low (26−50% yield), moderately high (51−75% yield), and high (76−100% yield). At the end of the Review, a conclusion will summarize our findings. We calculated overall statistics for the effectiveness of each bidentate phosphine with each nickel source for the complete review. These figures were generally determined by examining the test reaction of each reference to avoid number-skewing by counting substrate scopes and mechanistic studies. Therefore, each reference where a ligand was tested in one reaction only contributed one to that ligand’s count, even if the ligand was further used in other studies for the same reaction in the same paper. If different reactions were studied in the same article, such as a Suzuki and Heck reaction, the ligands were counted multiple times. This system gives an idea of ligand usage based on the number of different reaction classes instead of the number of times each ligand is used within each reference. 9 In terms of scope, this Review will not cover chelating bisamines or bisimines except when directly compared to the effectiveness of bidentate phosphines. Precatalysts, such as (dppe)NiCl 2 and (dppp)NiCl 2 (DPPP = 1,3-bis- (diphenylphosphino)propane), are not included except for cases where a free phosphine is also added to the reaction. Despite their commonality, these complexes are excluded because we are most interested in the effect of ligand exchange on the formation of an active catalyst, and these (phosphine)- NiCl2 complexes are theorized to become catalytically active through a reduction mechanism without a ligand exchange. Therefore, including these complexes would increase the complexity of our Review to an unacceptable level. Also, reactions only involving phosphite ligands, including bidentate phosphites, are not included and have been reviewed elsewhere.92 Bidentate phosphines with an amine added will also not be included. The structures of the ligands in this Review can be found in Chart 1. An aspect of any review which is worth noting is that the raw information conveyed by the authors is entirely dependent on prior publications. This factor places an onus on researchers to ensure that their data are reliable and well-supported. Throughout this Review, we limit speculation as much as possible and convey mechanistic findings where appropriate. Many of the conclusions drawn in this Review are based on single yields from single time points of test reactions, which emphasizes the importance of these seemingly preliminary results in the grand scope of research. We were able to draw a few conclusions from the vast number of references surveyed for this work. First, cross-coupling reactions are less sensitive to potential (phosphine)2Ni formation as compared to other modes of reactivity, such as cycloadditions. This observation is exemplified by the fact that many catalytic cross-coupling 10 reactions exist where DPPE and DPPP, bidentate phosphines which form (phosphine)2Ni with Ni(cod)2, are successful in creating an active catalyst with Ni(cod)2, resulting in high yields of products. Also, in these studies, a 2:1 loading of DPPE or DPPP with Ni(cod)2 was found to only slightly reduce efficacy. These results suggest that (phosphine)2Ni complexes may possess more extensive and complex reactivity patterns, and future research from our group focuses on this discrepancy. It is important to keep in mind also that this republication of the review is a condensed form, focusing not on the complete scope of the review but making an example of just some of the sub reactions investigated, as an almost proof of concept of what information the review can distribute. The complete review, “Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis” can be found in ACS’ Chemical Reviews Journal.579 LITERATURE REVIEW 4.1 HYDROGENATION, H2 Hydrogenation, the process of adding H2 across a double or triple bond, is a critical reaction given the general reactivities of olefins and other unsaturated bonds and the general stability and prevalence of alkanes. A typical path in organic synthesis involves connecting the desired atoms in the correct order using olefin reactivity and then hydrogenating the olefin as a final step to form the right product, particularly in enantioselective fashion. Common hydrogenating agents include the Lindlar catalyst, 11 which reduces alkynes to alkenes, and palladium on carbon (Pd/C), which reduces both alkynes and alkenes to alkanes.493−496 Asymmetric catalysis is also fundamental in hydrogenation because the reduction of alkynes or alkenes to alkanes forms a sp3-hybridized center, exemplified by the work of Noyori and others.497−499 With the push to obtain more earth-abundant catalysts, nickel has been studied in hydrogenation both heterogeneously500−503 and homogeneously. Kito, Yoshinaga, and co-workers used (−)-DIOP and NiCl2 (1:1), along with Et3N, andH2 as the hydrogen source, for a low yielding asymmetric hydrogenation of ethyl α-methylcrotonate.504 Jessop and co-workers found that a combination of DCPE and NiCl2 (1.5:1) is the most efficient catalyst system out of a wide array tested for CO2 hydrogenation activity.505 In 1998, Bouwman and co-workers studied a hydrogenation of 1-octene catalyzed by Ni(OAc)2 and different chelating phosphines (eq 174). DCPP, DCPE, and o-OMe-DPPP give higher activity, and others were lower (Table 20, entries 1−10). 12 13 14 15 The activities of these ligands were measured in TON rather than in the yields of products.506 Ten years later, a hydrogenation of α-amino-β-ketoester hydrochlorides was published by Hamada and co-workers. Ni(OAc)2·4H2O is used as the Ni source, with H2 as the hydrogen source. To make the reaction asymmetric, the researchers tested seven different Josiphos ligands, wherein SL-J001-1 gives the highest yield and ee (eq 175) (Table 21, entry 1).507 The next year, Hamada and co-workers published the same reaction with better diastereoselectivity, achieved through the use of an achiral ligand, and enantioselectivity, obtained through catalyzed in 88% yield with 99% ee using Ni(OAc)2 and (S)-binapine (eq 176) (Table 22, entry 7).509 Another related hydrogenation was published by Lv and coworkers,510 who used Ni(OAc)2 and bidentate phosphines for a hydrogenation of tetrasubstituted fluorinated enamides. A 99% yield is observed with (S)-binapine. (Rc,Sp)-Duanphos provides a 72% yield, and (R)-BINAP gives an 88% yield, and (S,S)Phen-Duphos and (S,S)-Me-Duphos give trace yields. The reaction was optimized with (S)-binapine to a 99% yield and 99% ee (eq177).510 This research was extended to hydrogenation of betaacylaminonitroolefins, with binapine again having the highest yield and ee511 and also to beta-(acylamino)acrylates.512 Chirik and co-workers513 tested a hydrogenation of ethyl β-methyl cinnamate catalyzed by Ni(OAc)2 and bidentate phosphines. A library of 192 phosphines was narrowed down to (S,S)-Me-Duphos having the highest ee (eq 178).513 16 17 4.2. Transfer Hydrogenation Transfer hydrogenation is an atom-economical and facile method of hydrogenating a substrate without resorting to gaseous H2 as a hydrogen source, sometimes alleviating difficulties caused by high-pressure reactions. As with other hydrogenation reactions, transfer hydrogenation has been accomplished with both heterogeneous514,515 and homogeneous516−518 catalysis. In the scope of our Review, Ni(cod)2, Ni(OAc)2, (dme)NiBr2, and (dme)NiCl2 have been used as Ni sources. Many researchers have used chiral ligands to induce asymmetric catalysis. A figure of the chiral ligand structures is included for reference. 4.2.1. Ni(cod)2 In 2016, a report was published by Garcia and co-workers of a transfer hydrogenation from ethanol to acetophenone catalyzed by Ni(cod)2 and bidentate phosphines 18 (eq 179). After establishing that DCPE (Table 23, entry 3), 1,2bis(diisopropylphosphino)ethane (DIPPE) (Table 23, entry 1), and DTBPE (Table 23, entry 2) lead to the highest conversion, yield, and selectivity, the researchers synthesized ((phosphine)-Ni(μ-H))2 complexes with each ligand and tested these complexes in the transfer hydrogenation study. The authors observed that these catalysts are not as active as the Ni(cod)2 /phosphine systems (Table 23, entries 7−9). DPPE is also low yielding in this reaction, possibly due to the formation of (dppe)2Ni. Interestingly, the ligand scope shows the potential power of changing the substituents of the bidentate phosphine to alkyl groups. DCPE, DIPPE, and DTBPE are all highly capable, while DPPE is not. Also, only smaller ligands with small natural bite angles ∼90° are active, as use of DPPF results in no conversion despite it forming (dppf)Ni(cod) with Ni(cod)2.519 Using DIPPE and Ni(cod)2 (2:1), the same group performed a similar transfer hydrogenation of benzil but used water and a silane as the hydrogen donor (eq 180). The proposed mechanism includes the formation of (dippe)2Ni, followed by the replacement of one of the DIPPE ligands with the ketone. The researchers also tested DCPE (2:1) and found that, while DIPPE requires a slightly higher temperature, the results are mostly the same.520 19 An asymmetric transfer hydrogenation of 4-fluoroacetophenone gives a high conversion with (S,S)-1,2-bis(2,5-diisopropylphospholan-1-yl)ethane ((S,S)-iPr-en-Duphos) and (S,S)-iPr-Duphos, along with a moderate ee. (S)-BINAP is unreactive and (S,S)-1,1′ bis(2,5-diethylphospholano)-ferrocene ((S,S)-Et-Ferrocelane) leads to a lower conversion and ee.520 The research was extended to catalytic transfer hydrogenation of benzonitriles, and a 3:3:2:1 ratio of Ni(cod)2:DCPE: DCPEO: DCPEO2 (where DCPEO is dicyclohexyl(2-(dicyclohexylphosphino)ethyl)phosphine oxide and DCPEO2 is ethane1,2-diylbis(dicyclohexylphosphine oxide)) is the most effective catalyst system due to less favorable binding of the phosphine oxide to the nickel center.521 20 4.2.2. Ni(OAc)2. Zhou and co-workers studied an asymmetric transfer hydrogenation of dehydro-βacetamidobutyrate (eq 181). The most active ligands give quantitative or near quantitative yields with a range of ee values (Table 24, entries 1,4, 10, and 11). This reaction is instructive in showing how a small change in ligand can completely inhibit product formation. For example, (R,R)-Me-Duphos gives a moderate yield (Table 24, entry 6), but (R,R)-Et-Duphos and (R,R)-iPr-Duphos are completely unreactive (Table 24, entries 7−8). The same goes for the addition of phenyl rings to the backbone of (1S)-Tangphos, which forms (1S)-Duanphos and decreases the yield substantially (Table 24, entries 2−3).522 4.2.3. (dme)NiBr2 Zhou and co-workers also studied a transfer hydrogenation of ethyl (E)-3-phenylbut-2enoate catalyzed by (dme)NiBr2 (eq 182). Ineffective ligands include some, such as (S)- 21 binapine (Table 25, entry 1), (R)-QuinoxP*(Table 25, entry 9), and SL-J003-1 (Table 25, entry 10), which are highly effective with Ni(OAc)2. (R,R)-Me-Duphos gives the highest yield (Table 25, entry 6), and the researchers further optimized the reaction to give a quantitative yield. Similar to the above example (eq 182), a small change in the ligand, such as going from (R,R)-Me-Duphos to (R,R)-Et-Duphos, completely suppresses product formation (Table 25, entries 6−7).523 Zhou and co-workers524 also used (dme)NiBr2 and chiral bidentate phosphines in a transfer hydrogenation of α,β-unsaturated esters (eq 183). Use of (R,R)-iPr-Duphos results in a 44% yield and (R)-QuinoxP* results in a 62% yield. (R,R)-Me-Duphos and (R,R)-Me-en-Duphos both lead to 99% yields. (R,R)-Ph-en-Duphos, (1S)-Tangphos, and (1S)-Duanphos also give high yields. This reaction is interesting in the discrepancy between Ni(II) sources, from a 62% yield using Ni(OTf)2 (Table 26, entry 4) to a 99% yield using (dme)NiBr2 (Table 26, entry 1).524 Zhou and co-workers524 also used (dme)NiBr2 and chiral bidentate phosphines in a transfer hydrogenation of α,β-unsaturated esters (eq 183). Use of (R,R)-iPr-Duphos results in a 44% yield and (R)-QuinoxP* results in a 62% yield. (R,R)-Me-Duphos and (R,R)-Me-en-Duphos both lead to 99% yields. (R,R)-Ph-en-Duphos, (1S)-Tangphos, and 22 (1S)-Duanphos also give high yields. This reaction is interesting in the discrepancy between Ni(II) sources, from a 62% yield using Ni(OTf)2 (Table 26, entry 4) to a 99% yield using (dme)NiBr2 (Table 26, entry 1).524 4.2.4. (dme)NiCl2. Finally, Zhou and co-workers525 also studied a transfer hydrogenation of a hydrazine from formic acid catalyzed by (dme)NiCl2 and a chelating phosphine. (R,R)-iPr-Duphos, (R)-BenzP*, (R)-QuinoxP*, (S)-binapine, (R)-1-((Sp)-2-(dicyclohexylphosphino)ferrocenyl)ethyldi-tert-butylphosphine (SL-J009-1), and SL-J003-1 are the most effective ligands, while (R,R)-Me-Ferrocelane gives no yield.525 23 CONCLUSION Nickel is becoming more common in both catalytic and stoichiometric reactions. The rapid growth does not look to slow down, particularly as the scientific community continues to push toward the use of more abundant materials. As the prevalence of nickel continues to expand, those who use it will benefit from an understanding of its properties and reactivity, eventually allowing distinctive tailoring of reaction conditions to give the desired product. Also, an essential goal in nickel catalysis is to maximize the amount of catalytically active metal in the solution. Achieving this aim will lower the generally high catalyst loadings in nickel-catalyzed reactions, which would assist arguments that a lower cost of nickel is beneficial as compared to palladium. This challenge is formidable and will not be overcome without significant research and work. With this contribution, we have made progress toward the overall understanding of the reactivity of nickel with bidentate phosphines. As stated previously, Ni(cod)2 is the most used nickel source with bidentate phosphines in catalytic reactions. According to our counting system, 549 overall examples exist of Ni(cod)2 being tested, which is a 5-fold increase over the following most common sources Ni(acac)2 and Ni(OAc)2 with 112 and 117 reports, respectively. With Ni(cod)2, DPPE is the most common ligand used with 53 reports. The commonality stems from DPPE generally being the one bidentate phosphine screened in a reaction where monodentate phosphines are the most effective. Other ligands such as DCPE, with 43 reports, DPPP, with 37, DPPB, with 41, BINAP in all its forms, with 44, and DPPF, with 43, are right behind DPPE in terms of usage. Xantphos is also close, having 26 24 references. In terms of the effectiveness of common bidentate phosphines with Ni(cod)2, Figure 15 provides a snapshot. It is clear that some ligands are more effective than others in reactions catalyzed by Ni(cod)2. Much of the focus of the review is on the efficacy of DPPE and DPPP with Ni(cod)2, and the calculated statistics show that nearly half of the experiments attempted with these two ligands and Ni(cod)2 result in low product yields. Both of these ligand’s form (phosphine)2Ni complexes, which, while reactive in some instances, are certainly less reactive than (phosphine)Ni(cod) complexes. The most successful ligands overall are DCPE, DPPB, BINAP, and DPPF. DCPE and DPPF form only (phosphine)Ni(cod) with Ni-(cod)2, reflecting the success rate of catalytic reactions, particularly for DCPE. DPPB is widely used in cycloaddition chemistry, and it forms (dppb)Ni(cod) in a 99:1 ratio with (dppb)2Ni when reacted with Ni(cod)2.42 BINAP forms more (binap)2Ni, but the success rate is still high. An interesting factor is a discrepancy in reactivity between catalytic cross-coupling reactions and other forms of catalytic reactions. Many of the high-yielding reactions using Ni(cod)2 and either DPPE or DPPP as catalyst systems come in the form of cross-coupling reactions. Conversely, many of the low yielding reactions using Ni(cod)2 and these two ligands occur in catalytic cycloaddition reactions. The pattern observed shows that (phosphine)2Ni complexes may be activated by a step-in mechanism of cross-coupling reactions. We hypothesize that with specific reagents, (phosphine)2Ni compounds can perform oxidative addition, and are actively studying this topic. Also, while DPPE and DPPP may be consistently unreactive in Ni-catalyzed cycloaddition chemistry, they should not be ignored in Ni-catalyzed cross-coupling. An essential set of ligands not yet 25 mentioned in the conclusion are chiral bidentate phosphines. Beyond Me-Duphos,76 DIOP,79 and (R)- and (S)-BINAP,49,172,256 chiral phosphines have not been studied for their reactivity with Ni(cod)2 or any Ni(II) complex. In particular, the reactivity of Ni(cod)2 with the oft used Josiphos set of ligands has not been examined, likely due to the high expense of the different ligands. However, with the efficacy of Josiphos ligands having been shown in our review, we feel that the reactivity of Josiphos ligands with Ni(cod)2 is an important area to explore in order to minimize the amount of costly ligand used in attempted catalytic transformations. Patterns and trends with Ni(II) complexes are harder to discern. The difficulty comes from the lack of understanding of relative rates of reduction as compared to ligand exchange and oxidative reactions from catalytic cycles. Researchers have published results where (phosphine)2Ni is formed from the combination of a Ni(II) complex, a reductant, and a bidentate phosphine.323,576−578 The role of this reactivity in catalysis, however, is unclear. Of the reactions studied here, borylation reactions catalyzed by (phosphine)NiCl2 along with an added free bidentate phosphine seem to be a likely area where (phosphine)2Ni complexes could form during a catalytic reaction. However, this speculation has not yet been supported by concrete results. As the field of Ni-catalyzed reactions with bidentate phosphines continues to grow, this contribution will assist in guiding researchers to combinations of metal and ligand which are more likely to form a catalytically active species. Knowledge of the effects of active catalyst formation will help to prevent unnecessary screenings from taking up time and materials for researching reactions that have a better chance of resulting in higher yields, rather than using the time on catalyst 26 systems doomed to fail from the beginning. The use of the hydrogenation chapter as the excerpt shows this utility, and we hope that one takes the time to also look at the completed publication to see the further extended applications of the bidentate phosphine ligand system. Also, we will conduct studies of the reduction of (phosphine)-NiX2 complexes to active catalysts, which is surprisingly sparse in its dedicated research. Results will be published in due course. 27 ASSOCIATED CONTENT *Supporting Information The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemrev.9b00682. ACKNOWLEDGMENTS We gratefully acknowledge the National Institute of Health (GM076125) for financial support. AUTHORS Andrew L. Clevenger − Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States Ryan M. Stolley − Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States Justis Aderibigbe − Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States Complete contact information is available at: https://pubs.acs.org/10.1021/acs.chemrev.9b00682 NOTES The authors declare no competing financial interest. 28 REFERENCES (1) Rej, S.; Chatani, N. Rhodium-Catalyzed Csp2- or Csp3-H Bond Functionalization Assisted by Removable Directing Groups. Angew. Chem., Int. Ed. 2019, 58, 8304−8329. (2) Thoke, M. B.; Kang, Q. Rhodium-Catalyzed Allylation Reactions. Synthesis 2019, 51, 2585−2631. (3) Rhodium Catalysis, 1st ed.; Springer International Publishing: Switzerland, 2018; Vol. 61, p 288. (4) Iridium Catalysis, 1 ed.; Springer-Verlag: Switzerland, 2011. (5) Choinopoulos, I. 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Stolley, Justis Aderibigbe, and Janis Louie Chemical Reviews 2020 120 (13), 6124-6196 DOI: 10.1021/acs.chemrev.9b00682 Copyright 2021 American Chemical Society 62 Name of Candidate: Justis Aderibigbe Birth date: September 15, 1999 Birth place: Wichita Falls, TX Address: 1666 East Garfield Ave SLC, Utah, 84105