Functionalization of Pentaphosphorus Cations by Complexation.

The chemistry of polyphosphorus cations has rapidly developed in recent years, but their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P R ] cations with cyclopentadienyl metal complexes. The reaction of [Cp Fe(μ-Br)] (Cp =C (C H -4-Et) ) with [P R ][GaCl ] (R=iPr and 2,4,6-Me C H (Mes)) afforded bicyclo[1.

Versatile Coordination Modes of Triphospha-1,4-pentadiene-2,4-diamine.

1,3,5-Triphospha-1,4-pentadiene-2,4-diamine reacts with [M(CO)L] (M = Mo, L = nbd (norbornadiene); M = W, L = 2 CHCN) to give the chelate complexes [M(CO)(PMes{C(NHCy)PMes}-κ P ,P)]. In contrast, an unusual intramolecular rearrangement occurred with [Cu(CHCN)]PF leading to the dimeric copper(I) complex [Cu(CNCy){PHMesPMesC(NHCy)PMes-κ P ,P}](PF). The mechanism of the rearrangement was supported by quantum-mechanical calculations.

A Sixteen-Membered Au P Macrocycle Based on Gold(I) and Diphospha(III)guanidine.

The reaction of cyclo-P Mes C(NCy) (1) with two equivalents of [AuCl(tht)] (tht=tetrahydrothiophene) resulted in the formation of unusual sixteen-membered Au-P macrocycle 2. This macrocycle contains diphospha(III)guanidinate as a coordinating ligand, which is formed by P-P bond cleavage of 1. Macrocycle 2 was characterized by multinuclear NMR spectroscopy, mass spectrometry and X-ray crystallography.

Unusual Reactivity of Sodium Tetramesityltetraphosphanediide towards Cyclohexyl Isocyanide.

The reaction of [Na (thf) (P Mes )] (Mes=2,4,6-Me C H ) with cyclohexyl isocyanide (2:5) resulted in the formation of the heterocyclic N-(tetramesityltetraphosphacyclopentylidene)cyclohexylamine [cyclo-{P Mes C(NCy)}] (2) (30-35 %), the unusual 1,3,5-triphospha-1,4-pentadiene (3) (40-45 %), and small amounts of the dimeric iminomethylidenephosphane cyclo-{PMesC(NCy)} (4). With catalytic amounts of AgBF , 2 was the major product. The reaction of 2 with [CuBr(SMe )] (1:1) produced bromido-bridged dimeric Cu complex 5.

Electrophile-induced nucleophilic substitution of the nido-dicarbaundecaborate anion nido-7,8-C2B9H12- by conjugated heterodienes.

Substitution of the dicarbaundecaborate anion nido-7,8-C2B9H12(-) (1) by precise hydride abstraction followed by nucleophilic attack usually leads to symmetric products 10-R-nido-7,8-C2B9H11. However, thioacetamide (MeC(S)NH2) as nucleophile and acetone/AlCl3 as hydride abstractor gave asymmetric 9-[MeC(NHiPr)S]-nido-7,8-C2B9H11 (2), whereas N,N-dimethylthioacetamide (MeC(S)NMe2) gave the expected symmetric 10-[MeC(NMe2)S]-nido-7,8-C2B9H11 (4). For the formation of 2, acetone and thioacetamide are assumed to give the intermediate MeC(S)N(CMe2) (3), which then attacks 1 with formation of 2.