Chemistry of metal hydrides

Christian, D.F.; Clark, H. C.; Stepaniak, R. F.

doi:10.1016/s0022-328x(00)80742-1

Cited by 45 publications

(8 citation statements)

References 23 publications

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“…The five-coordinate complex 9 is isolated in almost 50 % yield from the reaction between the isocyanide (tBuNC) and complex 6 (Scheme 3). The insertion of isocyanide into a PtÀH bond has been observed, [15] but in this case, there was no evidence that this reaction type occurs. Instead, a stannaborate ligand migrates to another platinum center.…”

Section: Resultsmentioning

confidence: 71%

“…the isocyanide CN in complex 7, which indicates an increase in the CN force constant with respect to that of uncoordinated isocyanide (2134 cm À1 ). [14] Since the complexes trans-[(Et 3 P) 2 PtH(CNMe)][ClO 4 ] (2270 cm À1 ), [15] trans-[(Et 3 P) 2 PtH(CNMe)][SO 3 F] (2238 cm À1 ), [15] and trans-[(Et 3 P) 2 PtCl(CNtBu)][ClO 4 ] (2211 cm À1 ), [14,16] which have a hydride or chloride ligand trans to the isocyanide ligand, exhibit a similar value for the CN force constant, it is difficult to discuss the trans influence on the basis of these data.…”

Section: Resultsmentioning

confidence: 99%

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Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

et al. 2001

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Three stannaborate complexes of platinum(II) and a novel stannoborate palladium(II) derivative have been prepared in excellent yield. The tin transition metal bond is formed through nucleophilic substitution and the resulting complexes [Bu3MeN] [trans-[(Et3P)2Pt(SnB11H11)H]] (6), [trans-[(Et3P)2Pt(SnB11H11)(CNtBu)]] (7), [Bu3MeN]2[trans-[(Et3P)2Pt(SnB11H11)2-(CNtBu)]] (8), and [Bu3MeN][(dppe)-Pd(SnB11H11)Me] (12) (dppe = 1,2-bis-(diphenylphosphanyl)ethane) were characterized by NMR spectroscopy and elemental analysis. In the cases of the zwitterion 7, the pentacoordinated complex 9, the palladium salt 12 and [(triphos)Pt(SnB11H11)] (10) (triphos = 1,1,1-tris(diphenylphosphanylmethyl)ethane), their solid-state structures are determined by X-ray crystal structure analyses. The trans influence of the [SnB11H11] ligand is evaluated from the results of the IR spectroscopy and X-ray crystallographic structures of complexes 6, 7, and 12. The dipole moment of the zwitterion 7 is calculated by density functional theory (DFT) methods. The alignment of the dipole moments of the polar molecules 7 and 12 in the solid state is discussed.

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Section: Resultsmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

et al. 2001

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“…When 13 CNAr Mes2 was employed, the terminal isocyanide carbon and both diazabutadiene carbons of 3 became isotopically enriched, as expected if the iminoformyl proton in 2 can reversibly migrate to the cobalt center and its η 6 -arene interaction can be labilized. 86,87,118,119 Ligand Substitution Chemistry of HCo(CNAr Mes2 ) 4 (1). In contrast to HCo[P(X) 3 ] 4 (X = OR, F) species, which are substitutionally inert, 52,53,55 HCo(CNAr Mes2 ) 4 (1) participated readily in ligand substitution reactions with a variety of 2edonor ligands to afford HCo(L)(CNAr Mes2 ) 3 (4 L ) derivatives (Scheme 6; L = CO, 76 CN-t-Bu, CNXyl, PMe 3 , PPh 3 ).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…This reaction afforded the η 6 -arene-coordinated, κ 1 - C -diazabutadiene complex Co(η 6 -(Mes)-κ 1 - C -C(C(H)NAr Mes2 )NAr Mes2 )(CNAr Mes2 ) ( 3 ; Scheme and Figure ), presumably through α-migration of the full [−C(H)NAr Mes2 ] unit into a terminal CNAr Mes2 ligand. When 13 CNAr Mes2 was employed, the terminal isocyanide carbon and both diazabutadiene carbons of 3 became isotopically enriched, as expected if the iminoformyl proton in 2 can reversibly migrate to the cobalt center and its η 6 -arene interaction can be labilized. ,,, …”

Section: Resultsmentioning

confidence: 99%

A Well-Defined Isocyano Analogue of HCo(CO)₄. 1: Synthesis, Decomposition, and Catalytic 1,1-Hydrogenation of Isocyanides

2016

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Reported here is the synthesis and characterization of the tetrakis(m-terphenyl isocyanide)cobalt hydride HCo(CNArMes2)4 (1; ArMes2 = 2,6-(2,4,6-Me3C6H2)2C6H3). Monohydride 1 serves as a well-defined isocyano analogue of the tetracarbonyl hydride HCo(CO)4. While tetrakis-phosphine analogues of HCo(CO)4 have been reported previously, these compounds have failed to exhibit a reactivity profile that can be compared and contrasted with HCo(CO)4 in a systematic fashion. Herein, HCo(CNArMes2)4 (1) is shown to be a readily accessed and reactive complex that allows for this comparison. For example, HCo(CNArMes2)4 (1) is found to decompose smoothly to the κ1 -C-iminoformyl complex Co(η6-(Mes)-κ1 C-C(H)NArMes2)(CNArMes2) (2). Kinetic analysis of this decomposition and that of the d 1-isotopomer DCo(CNArMes2)4 (1-d 1) revealed a unimolecular process characterized by a large primary k H/ k D isotope effect (3.2(6)) and no dependence on the presence of free CNArMes2. These data point to rate-limiting hydride α-migration and formation of the κ1-C-iminoformyl species [Co(κ1-C-C(H)NArMes2)(CNArMes2)3] as a critical intermediate. Indeed, ligand substitution reactions of HCo(CNArMes2)4 (1), as well as 13C-labeling experiments of the decomposition product 2, demonstrate that hydride α-migration is the dominant mechanistic feature of this system. Most notably, this behavior is in contrast with that of HCo(CO)4, for which it has been established that CO ligand dissociation is the initial mechanistic feature. Additional support for the critical role of hydride α-migration in HCo(CNArMes2)4 (1) was obtained by the development of catalytic CNArMes2 1,1-hydrogenation to form a stable and isolable methylenimine.

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“…Transition-metal hydrides have been shown to play a significant role in reactions related to energy storage and energy utilization. , These species have been proposed as valuable intermediates in many catalytic reactions. , For example, insertions of olefins, CO 2 , , or isocyanides lead to the corresponding alkyl, formate, or iminoformyl ligands that can be further functionalized to incorporate small-molecule building blocks into C 2+ organic products.…”

Section: Introductionmentioning

confidence: 99%

Reductive Carbonylation of Oxorhenium Hydrides Induced by Lewis Acids

et al. 2016

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Several oxorhenium hydride complexes with chelating diamidopyridine (DAP), diamidoamine (DAAm), and 2-mercaptoethyl sulfide (SSS) groups have been isolated and characterized. Adduct formation is observed when the DAP complex 1a is treated with the Lewis acid B(C6F5)3. However, treatment of 1a,b with B(C6F5)3 or BF3·OEt2 in the presence of CO results in reduction of the metal center by four electrons from Re(V) to Re(I).

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Chemistry of metal hydrides

Cited by 45 publications

References 23 publications

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

A Well-Defined Isocyano Analogue of HCo(CO)₄. 1: Synthesis, Decomposition, and Catalytic 1,1-Hydrogenation of Isocyanides

Reductive Carbonylation of Oxorhenium Hydrides Induced by Lewis Acids

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Chemistry of metal hydrides

Cited by 45 publications

References 23 publications

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

A Well-Defined Isocyano Analogue of HCo(CO)4. 1: Synthesis, Decomposition, and Catalytic 1,1-Hydrogenation of Isocyanides

Reductive Carbonylation of Oxorhenium Hydrides Induced by Lewis Acids

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A Well-Defined Isocyano Analogue of HCo(CO)₄. 1: Synthesis, Decomposition, and Catalytic 1,1-Hydrogenation of Isocyanides