Synthesis and Structure of Molybdenum and Tungsten Bisphosphine Carbonyl Dimers

Abstract

The synthesis of two bisphosphine ligands (R2P)2C6H4 with a para-disubstituted phenyl moiety is described (R = Cy (3), i-Pr (4)). Solutions of M(CO)3(C7H8) (C7H8 = η6-cycloheptatriene, M = Mo and W) and 3 or 4 were reacted under CO affording dimeric compounds of the general formula [M2(CO)8((R2P)2C6H4)2] (M = W, R = Cy (5); M = Mo, R = Cy (6); and M = W, R = i-Pr (7)). When the same reactions are carried out in the presence of H2, similar W−H2 analogues of the general formula [W2(CO)6((R2P)2C6H4)2(H2)2], R = Cy (8), R = i-Pr (9), can be observed by 1H and 31P NMR spectroscopy. Compounds 8 and 9 are not isolable, due to facile ligand redistribution forming 5 and 7, respectively.

1,2,3-Triazole based bisphosphine, 5-(diphenylphosphanyl)-1-(2-(diphenylphosphanyl)-phenyl)-4-phenyl-1H-1,2,3-triazole: an ambidentate ligand with switchable coordination modes

“…The ν CO features are similar to those of analogous complexes of the type cis -[M(CO) 4 (LL)] (M = Mo and W; LL = dppm and dppe). 15 …”

Fast and Tunable Phosphorescence from Organic Ionic Crystals

“…The target diphosphonium iodides 1-6 (Scheme 1) were conventionally synthesized from previously described tertiary bisphosphanes containing conjugated spacers (phenylene, [19] biphenyl, [19a] naphthalene, [20] and anthracene [21] ) by treatment with excess methyl iodide (see details in the Supporting Information). Derivative…”

Phosphines and related C–P bonded compounds

“…10 Stereochemical assignments relating to phosphines of the Taniaphos series (7), also prepared by the above route, have been corrected, following comments from other workers. 11 Other new phosphines also prepared in this way include a series of mono-and diphosphino-anthracenes (8), 12 the unsymmetrical 2,2 0 -bis (phosphino)diphenylamine (9), 13 the p-phenylenediphosphines (10), 14 the diphosphine (11), (capable of quaternisation at nitrogen to give water-soluble a Biomedical Research Centre, Sheffield Hallam University, Sheffield, UK S1 1WB Organophosphorus Chem., 2010, 39, 1-48 | 1 c The Royal Society of Chemistry 2010 15 and the tetraphosphines (12) that act as rigid scaffolds which prevent interactions of metal complexes with oxide supports. 16 A novel approach to 1,1 0 -bisphosphorus compounds is provided by treatment of diethyl chloromethylphosphonate (a carbene precursor) with butyl lithium, followed by a trialkylborane, which results in transfer of an alkyl group from boron to the carbenoid a-carbon.…”

“…17 The phosphonatophosphine (13, R ¼ SiMe 3 ) was prepared in a similar way by sequential treatment of diethyl methylphosphonate with LDA (2 mol), followed by chlorotrimethylsilane (1 mol) and chlorodiphenylphosphine (1 mol). 18 Direct lithiation of acidic carbon precursors has also been used in the synthesis of various heteroarylphosphines, including oligothienylphosphines, e.g., (14), 19 tris-2-(3methylindolyl)phosphine, (which demonstrates an ability to bind anions through the indole NH sites and coordinate to metals via phosphorus), 20 and the phosphinobipyrazole (15). 21 Depending on relative quantities of butyllithium and chlorodiphenylphosphine, 1-(1-naphthyl)-1H-benzimidazole undergoes monophosphination at either the 2-naphthyl or 2-benzimidazole positions, or at both, to give a diphosphine.…”