Search

The halogen-free synthesis of oligosilazanes has been observed upon dehydrocoupling silanes with ammonia at 25 °C using [( 2,6-iPr 2 Ph BDI)Mn(μ-H)] 2 . Extending this methodology to polymethylhydrosiloxanes afforded thermally robust polysiloxazane solids, and the dehydrocoupling of 1,3,5,7-tetramethylcyclotetrasiloxane with ammonia afforded a polysiloxazane having a weight-average molecular weight of 4300 g mol -1 . A representative oligosilazane has been applied to a copper surface and found to afford a 20 μm thick coating that resists corrosion after 24 h under water. Addition of ammonia to [( 2,6-iPr 2 Ph BDI)Mn(μ-H)] 2 allowed for characterization of the catalyst resting state, [( 2,6-iPr 2 Ph BDI)Mn(μ-NH 2 )] 2 , which has been found to mediate Si-N dehydrocoupling.

This article covers historical and recent efforts to catalyse the dehydrocoupling of amines and silanes, a direct method for Si-N bond formation that offers hydrogen as a byproduct. In some applications, this transformation can be used as a sustainable replacement for traditional aminosilane synthesis, which demands corrosive chlorosilanes while generating one equivalent of ammonium salt waste for each Si-N bond that is formed. These advantages have driven the development of Si-N dehydrocoupling catalysts that span the periodic table, affording mechanistic insight that has led to advances in efficiency and selectivity. Given the divergence in precursors being used, characterization methods being relied on, and applications being targeted, this article highlights the formation of monomeric aminosilanes separately from oligomeric and polymeric aminosilanes. A recent study that allowed for the manganese catalysed synthesis of perhydropolysilazane and commercial chemical vapor deposition precursors is featured, and key opportunities for advancing the field of Si-N dehydrocoupling catalysis are discussed.

Through the application of a redox-innocent aryl diimine chelate, the discovery and utilization of a cobalt catalyst, ( Ph 2 PPr ADI)Co, that exhibits carbonyl hydrosilylation turnover frequencies of up to 330 s -1 is described. This activity is believed to be the highest ever reported for metal-catalyzed carbonyl hydrosilylation.

It was recently discovered that ( Ph2PPr PDI)Mn (PDI = pyridine diimine) exists as a superposition of low-spin Mn(II) that is supported by a PDI dianion and intermediate-spin Mn(II) that is antiferromagnetically coupled to a triplet PDI dianion, a finding that encouraged the synthesis and electronic structure evaluation of late first row metal variants that feature the same chelate. The addition of Ph2PPr PDI to FeBr 2 resulted in bromide dissociation and the formation of [( Ph2PPr PDI)FeBr][Br]. Reduction of this precursor using excess sodium amalgam afforded ( Ph2PPr PDI)Fe, which possesses an Fe(II) center that is supported by a dianionic PDI ligand. Similarly, reduction of a premixed solution of Ph2PPr PDI and CoCl 2 yielded the cobalt analog, ( Ph2PPr PDI)Co. EPR spectroscopy and density functional theory calculations revealed that this compound features a high-spin Co(I) center that is antiferromagnetically coupled to a PDI radical anion. The addition of Ph2PPr PDI to Ni(COD) 2 resulted in ligand displacement and the formation of ( Ph2PPr PDI)Ni, which was found to possess a pendent phosphine group. Single-crystal X-ray diffraction, CASSCF calculations, and EPR spectroscopy indicate that ( Ph2PPr PDI)Ni is best described as having a Ni(II)-PDI 2- configuration. The electronic differences between these compounds are highlighted, and a computational analysis of Ph2PPr PDI denticity has revealed the thermodynamic penalties associated with phosphine dissociation from 5-coordinate ( Ph2PPr PDI)Mn, ( Ph2PPr PDI)Fe, and ( Ph2PPr PDI)Co.

This article highlights the utilization of phosphine-containing redox-active ligands for efficient hydrosilylation catalysis. Manganese, iron, cobalt, and nickel precatalysts featuring these chelates have been described and leading activities for carbonyl, carboxylate, and ester C-O bond hydrosilylation have been achieved. Mechanistic studies have provided insight into the importance of phosphine hemilability.

Refluxing Mo(CO) 6 in the presence of the phosphine-functionalized α-diimine ligand Ph2PPr DI allowed for substitution and formation of the dicarbonyl complex, ( Ph2PPr DI)Mo(CO) 2 . Oxidation with I 2 followed by heating resulted in further CO dissociation and isolation of the corresponding diiodide complex, ( Ph2PPr DI)MoI 2 . Reduction of this complex under a N 2 atmosphere afforded the corresponding bis(dinitrogen) complex, ( Ph2PPr DI)Mo(N 2 ) 2 . The solid-state structures of all three compounds were found to feature a tetradentate chelate and cis -monodentate ligands. Notably, the addition of CO 2 to ( Ph2PPr DI)Mo(N 2 ) 2 is proposed to result in head-to-tail CO 2 coupling to generate the corresponding metallacycle and ultimately a mixture of ( Ph2PPr DI)Mo(CO) 2 and the bis(oxo) dimer, [(κ 3 - Ph2PPr DI)Mo(O)(μ-O)] 2 . Computational studies have been performed to gain insight into the reaction and evaluate the importance of cis -coordination sites for selective head-to-tail CO 2 reductive coupling, CO deinsertion, disproportionation, and stepwise CO 2 deinsertion.

The electronic structure of a dimeric manganese hydride catalyst supported by β-diketiminate ligands, [(2,6-iPr2PhBDI)Mn(μ-H)]2, was investigated with density functional theory. A triple bond between the manganese centres was anticipated from simple electron-counting rules; however, calculations revealed Mn-Mn Mayer bond orders of 0.21 and 0.27 for the ferromagnetically-coupled and antiferromagnetically-coupled extremes, respectively. In accordance with experimentally determined Heisenberg exchange coupling constants of -15 ± 0.1 cm-1 (SQUID) and -10.2 ± 0.7 cm-1 (EPR), the calculated J0 value of -10.9 cm-1 confirmed that the ground state involves antiferromagnetic coupling between high spin Mn(ii)-d5 centres. The effect of steric bulk on the bond order was examined via a model study with the least sterically-demanding version of the β-diketiminate ligand and was found to be negligible. Mixing between metal- and β-diketiminate-based orbitals was found to be responsible for the absence of a metal-metal multiple bond. The bridging hydrides give rise to a relatively close positioning of the metal centres, while bridging atoms possessing 2p orbitals result in longer Mn-Mn distances and more stable dimers. The synthesis and characterization of the bridging hydroxide variant, [(2,6-iPr2PhBDI)Mn(μ-OH)]2, provides experimental support for these assessments.

The manganese hydride dimer, [( 2,6-iPr 2 Ph BDI)Mn(μ-H)] 2 , was found to mediate nitrile dihydroboration, rendering it the first manganese catalyst for this transformation. Stoichiometric experiments revealed that benzonitrile insertion affords [( 2,6-iPr 2 Ph BDI)Mn(μ-NCHC 6 H 5 )] 2 en route to N,N-diborylamine formation. Density functional theory calculations reveal the precise mechanism and demonstrate that catalysis is promoted by monomeric species.

The addition of lead to diphenyl diselenide in ethylenediamine (en) or pyridine (py) allowed for the observation of the solvento complexes, (en)Pb(SePh) 2 or (py) 2 Pb(SePh) 2 , respectively. Performing this reaction in dimethyl sulfoxide and subsequent crystallization was found to afford Pb(SePh) 2 . Inductively coupled plasma optical emission spectroscopy revealed a 1:2 lead to selenium ratio for all three complexes. Nuclear magnetic resonance spectroscopy confirms that Pb(SePh) 2 is readily solubilized by ethylenediamine, and electrospray ionization mass spectrometry supports the presence of Pb(SePh) 2 moieties in solution. Single-crystal X-ray diffraction analysis of the pyridine adduct, (py) 2 Pb(SePh) 2 , revealed a seesaw molecular geometry featuring equatorial phenylselenolate ligands. Crystals of Pb(SePh) 2 grown from dimethyl sulfoxide revealed one-dimensional polymeric chains of Pb(SePh) 2 . We believe that the lead(II) phenylselenolate complexes form via an oxidative addition reaction., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

N , N -Diborylamines have emerged as promising reagents in organic synthesis; however, their efficient preparation and full synthetic utility have yet to be realized. To address both shortcomings, an effective catalyst for nitrile dihydroboration was sought. Heating CoCl 2 in the presence of PyEt PDI afforded the six-coordinate Co(II) salt, [( PyEt PDI)CoCl][Cl]. Upon adding 2 equiv of NaEt 3 BH, hydride transfer to one chelate imine functionality was observed, resulting in the formation of (κ 4 - N,N,N,N - PyEt IP CHMe N EtPy )Co. Single-crystal X-ray diffraction and density functional theory calculations revealed that this compound possesses a low-spin Co(II) ground state featuring antiferromagnetic coupling to a singly reduced imino(pyridine) moiety. Importantly, (κ 4 - N,N,N,N - PyEt IP CHMe N EtPy )Co was found to catalyze the dihydroboration of nitriles using HBPin with turnover frequencies of up to 380 h -1 at ambient temperature. Stoichiometric addition experiments revealed that HBPin adds across the Co-N amide bond to generate a hydride intermediate that can react with additional HBPin or nitriles. Computational evaluation of the reaction coordinate revealed that the B-H addition and nitrile insertion steps occur on the antiferromagnetically coupled triplet spin manifold. Interestingly, formation of the borylimine intermediate was found to occur following BPin transfer from the borylated chelate arm to regenerate (κ 4 - N,N,N,N - PyEt IP CHMe N EtPy )Co. Borylimine reduction is in turn facile and follows the same ligand-assisted borylation pathway. The independent hydroboration of alkyl and aryl imines was also demonstrated at 25 °C. With a series of N , N -diborylamines in hand, their addition to carboxylic acids allowed for the direct synthesis of amides at 120 °C, without the need for an exogenous coupling reagent.

Catalysis is the second largest application for V after its use as an additive to improve steel production. Molecular complexes of vanadium(V) are particularly useful and efficient catalysts for oxidation processes; however, their ability to catalyze reductive transformations has yet to be fully explored. Here we report the first examples of polar organic functionality reduction mediated by V. Open-shell V III complexes that feature a π-radical monoanionic 2,2':6',2″-terpyridine ligand (Rtpy • ) - functionalized at the 4'-position (R = (CH 3 ) 3 SiCH 2 , C 6 H 5 ) catalyze mild and chemoselective hydroboration and hydrosilylation of functionalized ketones, aldehydes, imines, esters, and carboxamides with turnover numbers (TONs) of up to ∼1000 and turnover frequencies (TOFs) of up to ∼500 h -1 . Computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.

The phosphine-substituted α-diimine Ni precursor, (Ph2PPrDI)Ni, has been found to catalyze alkene hydrosilylation in the presence of Ph2SiH2 with turnover frequencies of up to 124 h-1 at 25 °C (990 h-1 at 60 °C). Moreover, the selective hydrosilylation of allylic and vinylic ethers has been demonstrated, even though (Ph2PPrDI)Ni is known to catalyze allyl ester C-O bond hydrosilylation. At 70 °C, this catalyst has been found to mediate the hydrosilylation of ten different gem-olefins, with turnover numbers of up to 740 under neat conditions. Prior and current mechanistic observations suggest that alkene hydrosilylation takes place though a Chalk-Harrod mechanism following phosphine donor dissociation.

The dimeric β-diketiminate manganese hydride compound, [( 2,6-iPr2Ph BDI)Mn(μ-H)] 2 , was prepared by treating [( 2,6-iPr2Ph BDI)Mn(μ-Cl)] 2 with NaEt 3 BH. This compound was characterized by single crystal X-ray diffraction and found to feature high-spin Mn centres that exhibit strong magnetic coupling by EPR spectroscopy. Once characterized, [( 2,6-iPr2Ph BDI)Mn(μ-H)] 2 was found to mediate the hydrosilylation of a broad scope of alkenes at elevated temperature. Aliphatic alkenes were found to undergo anti-Markovnikov hydrosilylation, while the hydrosilylation of styrenes using [( 2,6-iPr2Ph BDI)Mn(μ-H)] 2 afforded Markovnikov's product. Importantly, this catalyst has also been employed for the cross-linking of industrially-relevant silicones derived from vinyl-terminated poly(dimethylsiloxane) and 1,2,4-trivinylcyclohexane with catalyst loadings as low as 0.05 mol%. To gain a mechanistic understanding of [( 2,6-iPr2Ph BDI)Mn(μ-H)] 2 -catalyzed olefin hydrosilylation, 4- tert -butylstyrene was added to [( 2,6-iPr2Ph BDI)Mn(μ-H)] 2 and conversion to the monomeric Mn alkyl complex, ( 2,6-iPr2Ph BDI)Mn(CH(CH 3 )(4- t BuPh)), was observed. Isolation of this secondary alkyl intermediate confirms that olefin insertion into the Mn-H bond dictates the observed regioselectivities. The importance of our mechanistic findings as they relate to recent advances in Mn hydrosilylation catalysis is described herein.

The synthesis of alkylphosphine-substituted α-diimine (DI) ligands and their subsequent addition to Ni(COD)2 allowed for the preparation of (iPr2PPrDI)Ni and (tBu2PPrDI)Ni. The solid state structures of both compounds were found to feature a distorted tetrahedral geometry that is largely consistent with the reported structure of the diphenylphosphine-substituted variant, (Ph2PPrDI)Ni. To explore and optimize the synthetic utility of this catalyst class, all three compounds were screened for benzaldehyde hydrosilylation activity at 1.0 mol% loading over 3 h at 25 °C. Notably, (Ph2PPrDI)Ni was found to be the most efficient catalyst while phenyl silane was the most effective reductant. A broad scope of aldehydes and ketones were then hydrosilylated, and the silyl ether products were hydrolyzed to afford alcohols in good yield. When attempts were made to explore ester reduction, inefficient dihydrosilylation was noted for ethyl acetate and no reaction was observed for several additional substrates. However, when an equimolar solution of allyl acetate and phenyl silane was added to 1.0 mol% (Ph2PPrDI)Ni, complete ester C-O bond hydrosilylation was observed within 30 min at 25 °C to generate propylene and PhSi(OAc)3. The scope of this reaction was expanded to include six additional allyl esters, and under neat conditions, turnover frequencies of up to 990 h-1 were achieved. This activity is believed to be the highest reported for transition metal-catalyzed ester C-O bond hydrosilylation. Proposed mechanisms for (Ph2PPrDI)Ni-mediated carbonyl and allyl ester C-O bond hydrosilylation are also discussed.

We report the preparation and electronic structure determination of chelate-reduced Mn(I) compounds that are relevant to electrocatalytic proton reduction mediated by [( Ph2PPr PDI)Mn(CO)][Br]. Reducing [( Ph2PPr PDI)Mn(CO)][Br] with excess Na-Hg afforded a neutral paramagnetic complex, ( Ph2PPr PDI)Mn(CO). This compound was found to feature a low spin Mn(I) center and a PDI radical anion as determined by magnetic susceptibility measurement (1.97 μ B ), EPR spectroscopy ( S = 1 / 2 ), and density functional theory calculations. When [( Ph2PPr PDI)Mn(CO)][Br] was reduced with K-Hg, Mn(I) complexes with highly activated CO ligands were obtained. Recrystallization of the reduced product from diethyl ether solution allowed for the isolation of dimeric [(κ 4 - Ph2PPr PDI)Mn(μ-η 1 ,η 1 ,η 2 -CO)K(Et 2 O)] 2 (ν CO = 1710 cm -1 , 1656 cm -1 ), while methyl tert-butyl ether treatment afforded dimeric [(κ 4 - Ph2PPr PDI)Mn(μ-η 1 ,η 1 -CO)K(MTBE) 2 ] 2 (ν CO = 1695 cm -1 , MTBE = methyl tert-butyl ether). Addition of 18-crown-6 to these products, or conducting the K-Hg reduction of [( Ph2PPr PDI)Mn(CO)][Br] in the presence of 18-crown-6, allowed for the isolation of a monomeric example, (κ 4 - Ph2PPr PDI)Mn(μ-η 1 ,η 2 -CO)K(18-crown-6) (ν CO = 1697 cm -1 ). All three complexes were found to be diamagnetic and were characterized thoroughly by multinuclear 1D and 2D NMR spectroscopy and single crystal X-ray diffraction. Detailed analysis of the metrical parameters and spectroscopic properties suggest that all three compounds possess a Mn(I) center that is supported by a PDI dianion. Importantly, (κ 4 - Ph2PPr PDI)Mn(μ-η 1 ,η 2 -CO)K(18-crown-6) was found to react instantaneously with either HBF 4 ·OEt 2 or HOTf to evolve H 2 and generate the corresponding Mn(I) complex, [( Ph2PPr PDI)Mn(CO)][BF 4 ] or [( Ph2PPr PDI)Mn(CO)][OTf], respectively. These products are spectroscopically and electrochemically similar to previously reported [( Ph2PPr PDI)Mn(CO)][Br]. It is believed that the mechanism of [( Ph2PPr PDI)Mn(CO)][Br]-mediated proton reduction involves intermediates that are related to the compounds described herein and that their ambient temperature isolation is aided by the redox active nature of Ph2PPr PDI.

In recent years, interest in homogeneous manganese catalyst development has intensified because of the earth-abundant and nontoxic nature of this metal. Although compounds of Mn have largely been utilized for epoxidation reactions, recent efforts have revealed that Mn catalysts can mediate a broad range of reductive transformations. Low-valent Mn compounds have proven to be particularly effective for the hydrosilylation of carbonyl- and carboxylate-containing substrates, and this Account aims to highlight my research group's contributions to this field. In our initial 2014 communication, we reported that the bis(imino)pyridine-supported compound ( Ph2PPr PDI)Mn mediates ketone hydrosilylation with exceptional activity under solvent-free conditions. Silanes including Ph 2 SiH 2 , (EtO) 3 SiH, (EtO) 2 MeSiH, and (EtO)Me 2 SiH were found to partially reduce cyclohexanone in the presence of ( Ph2PPr PDI)Mn, while turnover frequencies of up to 1280 min -1 were observed using PhSiH 3 . This led us to evaluate the hydrosilylation of 11 additional ketones and allowed for the atom-efficient preparation of tertiary and quaternary silanes. At that time, it was also discovered that ( Ph2PPr PDI)Mn catalyzes the dihydrosilylation of esters (by way of acyl C-O bond hydrosilylation) to yield a mixture of silyl ethers with modest activity. Earlier this year, the scope of these transformations was extended to aldehydes and formates, and the observed hydrosilylation activities are among the highest obtained for any transition-metal catalyst. The effectiveness of three related catalysts has also been evaluated: ( Ph2PPr PDI)MnH, ( PyEt PDEA)Mn, and [( Ph2PEt PDI)Mn] 2 . To our surprise, ( Ph2PPr PDI)MnH was found to exhibit higher carboxylate dihydrosilylation activity than ( Ph2PPr PDI)Mn, while ( PyEt PDEA)Mn demonstrated remarkable carbonyl hydrosilylation activity considering that it lacks a redox-active supporting ligand. The evaluation of [( Ph2PEt PDI)Mn] 2 revealed competitive aldehyde hydrosilylation and formate dihydrosilylation turnover frequencies; however, this catalyst is significantly inhibited by pyridine and alkene donor groups. In our efforts to fully understand how ( Ph2PPr PDI)Mn operates, a thorough electronic structure evaluation was conducted, and the ground-state doublet calculated for this compound was found to exhibit nonclassical features consistent with a low-spin Mn(II) center supported by a singlet PDI dianion and an intermediate-spin Mn(II) configuration featuring antiferromagnetic coupling to PDI diradical dianion. A comprehensive mechanistic investigation of ( Ph2PPr PDI)Mn- and ( Ph2PPr PDI)MnH-mediated hydrosilylation has revealed two operable pathways, a modified Ojima pathway that is more active for carbonyl hydrosilylation and an insertion pathway that is more effective for carboxylate reduction. Although these efforts represent a small fraction of the recent advances made in Mn catalysis, this work has proven to be influential for the development of Mn-based reduction catalysts and is likely to inform future efforts to develop Mn catalysts that can be used to prepare silicones.

Addition of NaEt 3 BH to ( Ph2PPr DI)CoCl 2 affords the corresponding monohydride, ( Ph2PPr DI)CoH. X-ray diffraction and DFT calculations indicate that this compound possesses a radical monoanion α-DI chelate and a Co(ii) centre. Notably, ( Ph2PPr DI)CoH catalyzes the hydroboration of alkynes and dihydroboration of nitriles under mild conditions.

We recently reported a bis(imino)pyridine (or pyridine diimine, PDI) manganese precatalyst, ( Ph2PPr PDI)Mn (1), that is active for the hydrosilylation of ketones and dihydrosilylation of esters. In this contribution, we reveal an expanded scope for 1-mediated hydrosilylation and propose two different mechanisms through which catalysis is achieved. Aldehyde hydrosilylation turnover frequencies (TOFs) of up to 4900 min -1 have been realized, the highest reported for first row metal-catalyzed carbonyl hydrosilylation. Additionally, 1 has been shown to mediate formate dihydrosilylation with leading TOFs of up to 330 min -1 . Under stoichiometric and catalytic conditions, addition of PhSiH 3 to ( Ph2PPr PDI)Mn was found to result in partial conversion to a new diamagnetic hydride compound. Independent preparation of ( Ph2PPr PDI)MnH (2) was achieved upon adding NaEt 3 BH to ( Ph2PPr PDI)MnCl 2 and single-crystal X-ray diffraction analysis revealed this complex to possess a capped trigonal bipyramidal solid-state geometry. When 2,2,2-trifluoroacetophenone was added to 1, radical transfer yielded ( Ph2PPr PDI·)Mn(OC·(Ph)(CF 3 )) (3), which undergoes intermolecular C-C bond formation to produce the respective Mn(II) dimer, [(μ-O,N py -4-OC(CF 3 )(Ph)-4-H- Ph2PPr PDI)Mn] 2 (4). Upon finding 3 to be inefficient and 4 to be inactive, kinetic trials were conducted to elucidate the mechanisms of 1- and 2-mediated hydrosilylation. Varying the concentration of 1, substrate, and PhSiH 3 revealed a first order dependence on each reagent. Furthermore, a kinetic isotope effect (KIE) of 2.2 ± 0.1 was observed for 1-catalyzed hydrosilylation of diisopropyl ketone, while a KIE of 4.2 ± 0.6 was determined using 2, suggesting 1 and 2 operate through different mechanisms. Although kinetic trials reveal 1 to be the more active precatalyst for carbonyl hydrosilylation, a concurrent 2-mediated pathway is more efficient for carboxylate hydrosilylation. Considering these observations, 1-catalyzed hydrosilylation is believed to proceed through a modified Ojima mechanism, while 2-mediated hydrosilylation occurs via insertion.

In 5.0 M H2O/acetonitrile, [((Ph2PPr)PDI)MoO][PF6]2 produces H2 with 96% Faradaic efficiency at -2.5 V vs. Fc(+/0) and a rate of 55 s(-1). Reactivity studies and isolation of a Mo(ii) oxo intermediate, ((Ph2PPr)PDI)MoO, shed light on the H2 evolution mechanism.

Analysis of previously reported [((Ph2PPr)PDI)MoI][I] by cyclic voltammetry revealed a reversible wave at -1.20 V vs. Fc(+/0), corresponding to the Mo(ii)/Mo(i) redox couple. Reduction of [((Ph2PPr)PDI)MoI][I] using stoichiometric K/naphthalene resulted in ligand deprotonation rather than reduction to yield a Mo(ii) monoiodide complex featuring a Mo-C bond to the α-position of one imine substituent, (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoI. Successful isolation of the inner-sphere Mo(i) monoiodide complex, ((Ph2PPr)PDI)MoI, was achieved via reduction of [((Ph2PPr)PDI)MoI][I] with equimolar Na/naphthalene. This complex was found to have a near octahedral coordination geometry by single crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy revealed an unpaired Mo-based electron which is highly delocalized onto the PDI chelate core. Attempts to prepare a Mo(i) monohydride complex upon adding NaEt3BH to ((Ph2PPr)PDI)MoI resulted in disproportionation to yield an equimolar quantity of (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH and newly identified ((Ph2PPr)PDI)MoH2. Independent preparation of ((Ph2PPr)PDI)MoH2 was achieved by adding 2 equiv. NaEt3BH to [((Ph2PPr)PDI)MoI][I] and a minimum hydride resonance T1 of 176 ms suggests that the Mo-bound H atoms are best described as classical hydrides. Interestingly, ((Ph2PPr)PDI)MoH2 can be converted to (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoI upon iodomethane addition, while ((Ph2PPr)PDI)MoH2 is prepared from (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoI in the presence of excess NaEt3BH. Similarly, (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoI can be converted to (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH with 1 equiv. of NaEt3BH, while the opposite transformation occurs following iodomethane addition to (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH. Facile interconversion between [((Ph2PPr)PDI)MoI][I], (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoI, (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH, and ((Ph2PPr)PDI)MoH2 is expected to guide future reactivity studies on this unique set of compounds.

Reduction of 6-coordinate ((Ph2PPr)DI)FeBr₂ under N2 results in formation of the terminal dinitrogen complex, ((Ph2PPr)DI)FeN2. Heating this product to 75 °C allows for C-H and C-P activation of the chelate to generate the cisoid and transoid isomers of [(μ-PrPPh-κ(5)-P,N,N,Cγ,P-(Ph2PPr)DI(PrPPh))Fe]2. Mechanistic possibilities for this transformation are discussed.

Heating (THF)2MnCl2 in the presence of the pyridine-substituted bis(imino)pyridine ligand, (PyEt)PDI, allowed preparation of the respective dihalide complex, ((PyEt)PDI)MnCl2. Reduction of this precursor using excess Na/Hg resulted in deprotonation of the chelate methyl groups to yield the bis(enamide)tris(pyridine)-supported product, (κ(5)-N,N,N,N,N-(PyEt)PDEA)Mn. This complex was characterized by single-crystal X-ray diffraction and found to possess an intermediate-spin (S = (3)/2) Mn(II) center by the Evans method and electron paramagnetic resonance spectroscopy. Furthermore, (κ(5)-N,N,N,N,N-(PyEt)PDEA)Mn was determined to be an effective precatalyst for the hydrosilylation of aldehydes and ketones, exhibiting turnover frequencies of up to 2475 min(-1) when employed under solvent-free conditions. This optimization allowed for isolation of the respective alcohols and, in two cases, the partially reacted silyl ethers, PhSiH(OR)2 [R = Cy and CH(Me)((n)Bu)]. The aldehyde hydrosilylation activity observed for (κ(5)-N,N,N,N,N-(PyEt)PDEA)Mn renders it one of the most efficient first-row transition metal catalysts for this transformation reported to date.

Using a multistep synthetic pathway, a bis(imino)pyridine (or pyridine diimine, PDI) molybdenum catalyst for the selective conversion of carbon dioxide into methanol has been developed. Starting from ((Ph2PPr)PDI)Mo(CO), I2 addition afforded [((Ph2PPr)PDI)MoI(CO)][I], which features a seven-coordinate Mo(II) center. Heating this complex to 100 °C under vacuum resulted in CO loss and the formation of [((Ph2PPr)PDI)MoI][I]. Reduction of [((Ph2PPr)PDI)MoI][I] in the presence of excess K/Hg yielded (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH following methylene group C-H activation at the α-position of one PDI imine substituent. The addition of CO2 to (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH resulted in facile insertion to generate the respective η(1)-formate complex, (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)Mo(OCOH). When low pressures of CO2 were added to solutions of (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH containing pinacolborane, the selective formation of H3COBPin and O(BPin)2 was observed along with precatalyst regeneration. When HBPin was limited, H2C(OBPin)2 was observed as an intermediate and (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)Mo(OCOH) remained present throughout CO2 reduction. The hydroboration of CO2 to H3COBPin was optimized and 97% HBPin utilization by 0.1 mol % (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH was demonstrated over 8 h at 90 °C, resulting in a methoxide formation turnover frequency (TOF) of 40.4 h(-1) (B-H utilization TOF = 121.2 h(-1)). Hydrolysis of the products and distillation at 65 °C allowed for MeOH isolation. The mechanism of (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH mediated CO2 hydroboration is presented in the context of these experimental observations. Notably, (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH is the first Mo hydroboration catalyst capable of converting CO2 to MeOH, and the importance of this study as it relates to previously described catalysts is discussed.

Heating a 1:1 mixture of (CO)5MnBr and the phosphine-substituted pyridine diimine ligand, (Ph2PPr)PDI, in THF at 65 °C for 24 h afforded the diamagnetic complex [((Ph2PPr)PDI)Mn(CO)][Br] (1). Higher temperatures and longer reaction times resulted in bromide displacement of the remaining carbonyl ligand and the formation of paramagnetic ((Ph2PPr)PDI)MnBr (2). The molecular structure of 1 was determined by single crystal X-ray diffraction, and density functional theory (DFT) calculations indicate that this complex is best described as low-spin Mn(I) bound to a neutral (Ph2PPr)PDI chelating ligand. The redox properties of 1 and 2 were investigated by cyclic voltammetry (CV), and each complex was tested for electrocatalytic activity in the presence of both CO2 and Brønsted acids. Although electrocatalytic response was not observed when CO2, H2O, or MeOH was added to 1 individually, the addition of H2O or MeOH to CO2-saturated acetonitrile solutions of 1 afforded voltammetric responses featuring increased current density as a function of proton source concentration (icat/ip up to 2.4 for H2O or 4.2 for MeOH at scan rates of 0.1 V/s). Bulk electrolysis using 5 mM 1 and 1.05 M MeOH in acetonitrile at -2.2 V vs Fc(+/0) over the course of 47 min gave H2 as the only detectable product with a Faradaic efficiency of 96.7%. Electrochemical experiments indicate that CO2 promotes 1-mediated H2 production by lowering apparent pH. While evaluating 2 for electrocatalytic activity, this complex was found to decompose rapidly in the presence of acid. Although modest H(+) reduction activity was realized, the experiments described herein indicate that care must be taken when evaluating Mn complexes for electrocatalytic CO2 reduction.

Attempts to prepare low-valent molybdenum complexes that feature a pentadentate 2,6-bis(imino)pyridine (or pyridine diimine, PDI) chelate allowed for the isolation of two different products. Refluxing Mo(CO)6 with the pyridine-substituted PDI ligand, (PyEt)PDI, resulted in carbonyl ligand substitution and formation of the respective bis(ligand) compound ((PyEt)PDI)2Mo (1). This complex was investigated by single-crystal X-ray diffraction, and density functional theory calculations indicated that 1 possesses a Mo(0) center that back-bonds into the π*-orbitals of the unreduced PDI ligands. Heating an equimolar solution of Mo(CO)6 and the phosphine-substituted PDI ligand, (Ph2PPr)PDI, to 120 °C allowed for the preparation of ((Ph2PPr)PDI)Mo(CO) (2), which is supported by a κ(5)-N,N,N,P,P-(Ph2PPr)PDI chelate. Notably, 1 and 2 have been found to catalyze the hydrosilylation of benzaldehyde at 90 °C, and the optimization of 2-catalyzed aldehyde hydrosilylation at this temperature afforded turnover frequencies of up to 330 h(-1). Considering additional experimental observations, the potential mechanism of 2-mediated carbonyl hydrosilylation is discussed.

The reduction of ((Ph2PPr)PDI)MnCl2 allowed the preparation of the formally zerovalent complex, ((Ph2PPr)PDI)Mn, which features a pentadentate bis(imino)pyridine chelate. This complex is a highly active precatalyst for the hydrosilylation of ketones, exhibiting TOFs of up to 76,800 h(-1) in the absence of solvent. Loadings as low as 0.01 mol % were employed, and ((Ph2PPr)PDI)Mn was found to mediate the atom-efficient utilization of Si-H bonds to form quaternary silane products. ((Ph2PPr)PDI)Mn was also shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C-O bond. Electronic structure investigation of ((Ph2PPr)PDI)Mn revealed that this complex possesses an unpaired electron on the metal center, rendering it likely that catalysis takes place following electron transfer to the incoming carbonyl substituent.

Although bis(α-diimine)Ni complexes were prepared when amine-substituted chelates were added to Ni(COD)2, the incorporation of strong-field phosphine donors allowed the isolation of (κ(4)-N,N,P,P-DI)Ni hydrosilylation catalysts. The crystallographic investigation of two different (κ(4)-N,N,P,P-DI)Ni compounds revealed that the geometry about nickel influences the observed degree of α-diimine reduction.

The reduction of Triphos [PhP(CH(2)CH(2)PPh(2))(2)] iron halide complexes has been explored, yielding formally zerovalent (κ(3)-Triphos)Fe(κ(2)-Triphos) and (κ(3)-Triphos)Fe(κ(2)-Bpy). Electrochemical analysis, coupled with the metrical parameters of (κ(3)-Triphos)Fe(κ(2)-Bpy), reveal an electronic structure consistent with a π-radical monoanion bipyridine chelate that is antiferromagnetically coupled to a low spin, Fe(I) metal center.

The covalent attachment of tris(allyl)iridium to partially dehydroxylated gamma-alumina is found to proceed via surface hydroxyl group protonation of one allyl ligand to form an immobilized bis(allyl)iridium moiety, (=AlO)Ir(allyl)(2), as characterized by CP-MAS (13)C NMR, inductively coupled plasma-mass spectrometry, and Ir L(3) edge X-ray absorption spectroscopy. Extended X-ray absorption fine-structure (EXAFS) measurements taken on unsupported Ir(allyl)(3) and several associated tertiary phosphine addition complexes suggest that the eta(3)-allyl ligands generally account for an Ir-C coordination number of 2 rather than 3, with an average Ir-C distance of 2.16 A. Using this knowledge, combined EXAFS and X-ray absorption near-edge structure studies reveal that a small amount of Ir(0) is also formed upon reaction of Ir(allyl)(3) with the surface. It was found that the addition of either 2,6-dimethylphenyl isocyanide or carbon monoxide to the supported complex allows spectroscopic identification of the supported bis(allyl)iridium complexes, (=AlO)Ir(allyl)(2)(CNAr) [Ar = 2,6-(CH(3))(2)C(6)H(4)] and (=AlO)Ir(allyl)(2)(CO)(2), respectively. Although samples of the supported bis(allyl)iridium complex are active for the dehydrogenation of cyclohexane to benzene at temperatures between 180 and 220 degrees C, in situ temperature-programmed reaction XAFS and continuous-flow reactor studies suggest that Ir(0) nanoparticles, rather than a well-defined Ir(3+) complex, are responsible for the observed activity.

Addition of PMe3 to Mo2(allyl)4 afforded Mo2(allyl)4(PMe3)2, in which two of the allyl groups adopt an unprecedented micro2-eta1,eta3 bonding mode; theoretical studies elucidate the roles of the sigma- and pi-donor ligands in the interplay of metal-allyl and metal-metal bonding.

Sodium amalgam reduction of the aryl-substituted bis(imino)pyridine iron dibromide complex, ((Et)PDI)FeBr2 ((Et)PDI = 2,6-(2,6-Et2-C6H3N=CMe)2C5H3N), under a dinitrogen atmosphere in pentane furnished the bis(chelate)iron compound, ((Et)PDI)2Fe. Characterization by X-ray crystallography established a distorted four-coordinate iron center with two kappa2-bis(imino)pyridine ligands. Reducing the steric demands of the imine substituent to either a less sterically encumbered aryl ring (e.g., C6H4-4-OMe) or an alkyl group (e.g., Cy, iPr, cis-myrtanyl) also yielded bis(chelate) compounds from sodium amalgam reduction of the corresponding dihalide. Characterization of the compounds with smaller imine substituents by X-ray diffraction established six-coordinate, pseudo-octahedral compounds. In one case, a neutral bis(chelate)iron compound was prepared by reduction of the corresponding iron dication, [(PDI)2Fe]2+, providing chemical confirmation of electrochemically generated species that were previously reported as too reducing to isolate. Magnetic measurements, metrical parameters from X-ray structures, Mössbauer spectroscopy, and open-shell, broken symmetry DFT calculations were used to establish the electronic structure of both types (four- and six-coordinate) of neutral bis(chelate) compounds. The experimentally observed S = 1 compounds are best described as having high-spin ferrous (S(Fe) = 2) centers antiferromagnetically coupled to two bis(imino)pyridine radical anions. Thus, the two-electron reduction of the diamagnetic, low-spin complex [(PDI)2Fe]2+ to [(PDI)2Fe] is ligand-based with a concomitant spin change at iron.

Bis(imino)pyridine iron alkyl complexes bearing beta-hydrogens, ((iPr)PDI)FeR (((iPr)PDI = 2,6-(2,6-(i)Pr2-C6H3N=CMe)2C5H3N; R = Et, (n)Bu, (i)Bu, CH2 (cyclo)C5H 9; 1-R), were synthesized either by direct alkylation of ((iPr)PDI)FeCl (1-Cl) with the appropriate Grignard reagent or more typically by oxidative addition of the appropriate alkyl bromide to the iron bis(dinitrogen) complex, ((iPr)PDI)Fe(N2)2 (1-(N2)2). In the latter method, the formal oxidative addition reaction produced ((iPr)PDI)FeBr (1-Br), along with the desired iron alkyl, 1-R. Elucidation of the electronic structure of 1-Br and related 1-R derivatives by magnetic measurements, structural studies and NMR spectroscopy established high spin ferrous compounds antiferromagnetically coupled to chelate radical anions. Thus, the formal oxidative process is bis(imino)pyridine ligand-based (one electron is formally removed from each chelate, not the iron) during oxidative addition. The kinetic stability of each 1-R compound was assayed in benzene-d6 solution and found to produce a mixture of the corresponding alkane and alkene. The kinetic stability of the iron alkyl complexes was inversely correlated with the number of beta-hydrogens present. For example, the iron ethyl complex, 1-Et, underwent clean loss of ethane over the course of three hours, whereas the corresponding 1-(i)Bu compound had a half-life of over 12 h under identical conditions. The mechanism of the decomposition was studied with a series of deuterium labeling experiments and support a pathway involving initial beta-hydrogen elimination followed by cyclometalation of an isopropyl methyl group, demonstrating an overall transfer hydrogenation pathway. The relevance of such pathways to chain transfer in bis(imino)pyridine iron catalyzed olefin polymerization reactions is also presented.

Treatment of the bis(diisopropylphosphino)pyridine iron dichloride, ((iPr)PNP)FeCl2 ((iPr)PNP = 2,6-(iPr2PCH2)2(C5H3N)), with 2 equiv of NaBEt3H under an atmosphere of dinitrogen furnished the diamagnetic iron(II) dihydride dinitrogen complex, ((iPr)PNP)FeH2(N2). Addition of 1 equiv of PhSiH3 to ((iPr)PNP)FeH2(N2) resulted in exclusive substitution of the hydride trans to the pyridine to yield the silyl hydride dinitrogen compound, ((iPr)PNP)FeH(SiH2Ph)N2, which has been characterized by X-ray diffraction. The solid-state structure established a distorted octahedral geometry where the hydride ligand distorts toward the iron silyl. Both ((iPr)PNP)FeH2(N2) and ((iPr)PNP)FeH(SiH2Ph)N2 form eta2-dihydrogen complexes upon exposure to H2. The iron hydrides and the eta2-H2 ligands are in rapid exchange in solution, consistent with the previously reported "cis" effect, arising from a dipole/induced dipole interaction between the two ligands. Taken together, the spectroscopic, structural, and reactivity studies highlight the relative electron-donating ability of this pincer ligand as compared to the redox-active aryl-substituted bis(imino)pyridines.

Square planar iron methyl complexes containing bis(imino)pyridine (PDI) ligands have been prepared by reductive alkylation of the corresponding ferrous dichloride; dialkylation is observed upon treatment with a larger alkyl lithium.