Phosphorus phosphorus compounds with the coordination number 4
01 Jan 1977-pp 90-110
About: The article was published on 1977-01-01. It has received None citations till now. The article focuses on the topics: Phosphorus.
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TL;DR: In this paper, a hexamethylphosphoramide (HPHP) adduct of BF 3 and BCl 3 was shown to be capable of cleaving the boron-halogen bond in amine-haloboranes for the bromine and iodine species.
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3 citations
TL;DR: In this paper, the ionic complexes formed in the reactions of PF2(OR) with [Pt(C2H4)L2] and [Ir(CO)ClL2](L = PPh3; R = allyl).
Abstract: Ionic complexes [R·L]2[M(PF2O)4][M = Pt or Pd; L = NMe3. pyridine (py), or PPh3; R = allyl or Bun] and [R·L]2[cis-MCl2(PF2O)2](M = Pt or Pd; L = NMe3; R = allyl or Bun) have been obtained by treating [MCl2L2] with PF2(OR) at room temperature. Similar ionic complexes seen to be formed in the reactions of PF2(OR) with [Pt(C2H4)L2] and [Ir(CO)ClL2](L = PPh3; R = allyl). The products have been characterized by means of 1H, 13C, 19F, and 31P n.m.r. and i.r. spectroscopy, and elemental analysis.
3 citations
TL;DR: In this paper, a two-step carbonyl substitution reaction with tri-n-butylphosphine in decalin was studied, where the substitutions occurred by a dissociative mechanism involving the reactive intermediate [L(OC)3[graphic omitted]o(CO)3] which has a co-ordinatively unsaturated six-coordinate molybdenum atom.
Abstract: In the absence of light, di-µ-diethylphosphido-bis(tetracarbonylmolybdenum)(Mo–Mo), (I), undergoes a two-step carbonyl substitution reaction with tri-n-butylphosphine in decalin, giving [(Bu3P)(OC)3[graphic omitted]o(CO)4], (II), and [(Bu3P)(OC)3[graphic omitted]o(CO)3(PBu3)], (III). The substitution reaction does not go to completion in the presence of carbon monoxide and the kinetics of the forward and reverse reaction for each step have been studied. All the substitutions occur by a dissociative mechanism involving the reactive intermediate [L(OC)3[graphic omitted]o(CO)3](L = CO or PBu3) which has a co-ordinatively unsaturated six-co-ordinate molybdenum atom. Values of the competition ratio kco/kPBus for bimolecular attack on this intermediate, at 80 °C, range from 67.0 for L = CO to 2.62 × 104 for L = PBu3. Thus the co-ordinatively unsaturated metal centre shows an unexpected high sensitivity to the nature of the incoming ligand and to steric and/or electronic variations on the adjacent metal atom. The substitution of one CO group by PBu3 in (I) does not affect the rate of dissociation of CO, whereas (II) has a different rate of dissociation of PBu3 compared to (III). Activation parameters for the rate constants and competition ratios, together with equilibrium data, for these reactions are reported.
3 citations