Phosphine-nitrile ligands: the molecular structure of cis-2-diphenylphosphino-1-cyanocyclopentane and studies of the donor/acceptor properties of this and related ligands

Fredericks, E.J.; Gindling, M.J.; Kroll, Leroy C.; Storhoff, Bruce N.

doi:10.1016/0022-328x(94)87068-3

Cited by 4 publications

(4 citation statements)

References 30 publications

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“…However, as 132 has more rigid structure the final result is defined by 1-Diphenylphosphino-2-cyanocycloalkanes are the closest structure analogues of 2-cyanophenylphosphines. Thus, similar to the latter in the cis-isomer of 1-Ph2P-2-CN-C5H8 cyano group is directed towards the lone electron pair of the phosphorus atom [51]. All cyano-substituted cycloalkyl phosphines are less basic comparing with PPh3 but more basic compared to their acyclic analogues.…”

Section: Phosphinobenzonitriles and Phosphinocycloalkanecarbonitrilesmentioning

confidence: 95%

“…For the cyclopentane derivative both isomers were isolated in the individual state, for 1-diphenylphosphino-2-cyanocyclohexane -only cis-isomer [51]. The structure of cis-cyclopentyl phosphine was confirmed by the X-ray data, allowing to establish a correspondence between the position of corresponding signals in the NMR spectra and the space pattern of the compound.…”

Section: Addition Of P-h Phosphines To Cyano Substituted Olefins (Hydmentioning

confidence: 96%

“…Both cis and trans isomers of cycloalkylphosphines 141 form stable Pd(II) complexes 142 having trans-configuration [51]. Interaction of 141 with K2PtCl4 proceeds according to a similar fashion as was outlined for 2-cyanoarylphosphines [35] leading to trans-L2PtCl2 complexes which follows from coupling constant 1 JPtP (2524 Hz) [122b].…”

Section: Phosphinobenzonitriles and Phosphinocycloalkanecarbonitrilesmentioning

confidence: 98%

“…All cyano-substituted cycloalkyl phosphines are less basic comparing with PPh3 but more basic compared to their acyclic analogues. At that transisomer of 141a is more basic that the corresponding cis-141a (Table) [51].…”

Section: Phosphinobenzonitriles and Phosphinocycloalkanecarbonitrilesmentioning

confidence: 98%

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Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

Odinets¹,

Vinogradova²,

Matveeva³

et al. 2005

COC

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Synthetic approaches to both linear and cyclic cyano-substituted phosphines (P~CN-phosphines) found an industrial application as catalyst precursors, pesticides, herbicides, flame retardants, precursors of aminophosphines etc., are reported. The main synthetic routes include reduction of P=O containing precursors, alkylation of silylphosphines and metal phosphides by halogenoalkyl(aryl)carbonitriles, phosphorylation of the latter ones, decomposition of phosphonium salts and hydrophosphination of cyano-substituted olefins proceeding under non-catalytical conditions and with use of metal complex catalysis. Merits and demerits of each approach are discussed. Phosphines bearing cyano function as an additional coordination site show diverse coordination behavior depending on the phosphine structure and nature of the metal. Four main types of complexes are observed, namely those with P-monodentate coordination, with N-monodentate coordination and complexes where bidentate coordination mode of P and N atoms is realized either at the single metal atom or of bridged type between two different metal atoms. Thus coordination behavior of such P~CN-ligands relative to transition and non-transition metals, structure features of the complexes obtained and their application in catalytic processes are discussed.

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Section: Phosphinobenzonitriles and Phosphinocycloalkanecarbonitrilesmentioning

confidence: 95%

Section: Addition Of P-h Phosphines To Cyano Substituted Olefins (Hydmentioning

confidence: 96%

Section: Phosphinobenzonitriles and Phosphinocycloalkanecarbonitrilesmentioning

confidence: 98%

Section: Phosphinobenzonitriles and Phosphinocycloalkanecarbonitrilesmentioning

confidence: 98%

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Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

Odinets¹,

Vinogradova²,

Matveeva³

et al. 2005

COC

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Synthesis and study of phosphines incorporating 2-cyanophenyl groups and the X-ray structure of tris(2-cyanophenyl)phosphine

et al. 1999

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In Situ Formation of Ruthenium Catalysts for the Homogeneous Hydrogenation of Carbon Dioxide

et al. 2002

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A total of 44 different phosphines were tested, in combination with [RuCl(2)(C(6)H(6))](2) and three other Ru(II) precursors, for their ability to form active catalysts for the hydrogenation of CO(2) to formic acid. Half (22) of the ligands formed catalysts of significant activity, and only 6 resulted in very high rates of production of formic acid. These were PMe(3), PPhMe(2), dppm, dppe, and cis- and trans-Ph(2)PCH=CHPPh(2). The in situ catalysts prepared from [RuCl(2)(C(6)H(6))](2) and any of these 6 phosphine ligands were found to be at least as efficient as the isolated catalyst RuCl(O(2)CMe)(PMe(3))(4). There was no correlation between the basicity of monophosphines (PR(3)) and the activity of the catalysts formed from them. However, weakly basic diphosphines formed highly active catalysts only if their bite angles were small, while more strongly basic diphosphines had the opposite trend. In situ (31)P NMR spectroscopy showed that trans-Ru(H)(2)(dppm)(2), trans-RuCl(2)(dppm)(2), trans-RuHCl(dppm)(2), cis-Ru(H)(O(2)CH)(dppm)(2), and cis-Ru(O(2)CH)(2)(dppm)(2) are produced as the major metal-containing species in reactions of dppm with [RuCl(2)(C(6)H(6))](2) under catalytic conditions at 50 degrees C.

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Phosphine-nitrile ligands: the molecular structure of cis-2-diphenylphosphino-1-cyanocyclopentane and studies of the donor/acceptor properties of this and related ligands

Cited by 4 publications

References 30 publications

Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

Synthesis and study of phosphines incorporating 2-cyanophenyl groups and the X-ray structure of tris(2-cyanophenyl)phosphine

In Situ Formation of Ruthenium Catalysts for the Homogeneous Hydrogenation of Carbon Dioxide

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