Formation of a Hexaphosphido Cobalt Complex through P-P Condensation.

The reaction between diphosphorus derivatives [(Cl ImDipp )P2 (Dipp)]OTf (1[OTf]) and [(Cl ImDipp )P2 (Dipp)Cl] (1[Cl]) with the cyclotetraphosphido cobalt complex [K(18c-6)][(PHDI)Co(η4 -cyclo-P4 )] (2) leads to the formation of complex [(PHDI)Co{η4 -cyclo-P6 (Dipp)(Cl ImDipp )}] (3), which features an unusual hexaphosphido ligand [Cl ImDipp =4,5-dichloro-1,3-bis(2,6-diisopropylphenyl)imidazol-2-yl, Dipp=2,6-diisopropylphenyl, 18c-6=18-crown-6, PHDI=bis(2,6-diisopropylphenyl)phenanthrene-9,10-diimine]. Complex 3 was obtained as a crystalline material with a moderate yield at low temperature. Upon exposure to ambient temperature, compound 3 slowly transforms into two other compounds, [K(18c-6)][(PHDI)Co(η4 -P7 Dipp)] (4) and [(PHDI)Co{cyclo-P5 (Cl ImDipp )}] (5). The novel complexes 3-5 were characterized using multinuclear NMR spectroscopy and single-crystal X-ray diffraction. To shed light on the formation of these compounds, a proposed mechanism based on 31 P NMR monitoring studies is presented.

Transition-Metal-Mediated Functionalization of White Phosphorus.

Recently there has been great interest in the reactivity of transition-metal (TM) centers towards white phosphorus (P4 ). This has ultimately been motivated by a desire to find TM-mediated alternatives to the current industrial routes used to transform P4 into myriad useful P-containing products, which are typically indirect, wasteful, and highly hazardous. Such a TM-mediated process can be divided into two steps: activation of P4 to generate a polyphosphorus complex TM-Pn , and subsequent functionalization of this complex to release the desired phosphorus-containing product. The former step has by now become well established, allowing the isolation of many different TM-Pn products. In contrast, productive functionalization of these complexes has proven extremely challenging and has been achieved only in a relative handful of cases. In this review we provide a comprehensive summary of successful TM-Pn functionalization reactions, where TM-Pn must be accessible by reaction of a TM precursor with P4 . We hope that this will provide a useful resource for continuing efforts that are working towards this highly challenging goal of modern synthetic chemistry.

[3+2] Fragmentation of a Pentaphosphido Ligand by Cyanide.

The activation of white phosphorus (P4 ) by transition-metal complexes has been studied for several decades, but the functionalization and release of the resulting (organo)phosphorus ligands has rarely been achieved. Herein we describe the formation of rare diphosphan-1-ide anions from a P5 ligand by treatment with cyanide. Cobalt diorganopentaphosphido complexes have been synthesized by a stepwise reaction sequence involving a low-valent diimine cobalt complex, white phosphorus, and diorganochlorophosphanes. The reactions of the complexes with tetraalkylammonium or potassium cyanide afford a cyclotriphosphido cobaltate anion 5 and 1-cyanodiphosphan-1-ide anions [R2 PPCN]- (6-R). The molecular structure of a related product 7 suggests a novel reaction mechanism, where coordination of the cyanide anion to the cobalt center induces a ligand rearrangement. This is followed by nucleophilic attack of a second cyanide anion at a phosphorus atom and release of the P2 fragment.

Synthesis of a Cyclic Co2Sn2 Cluster Using a Co- Synthon.

[Ar'SnCo]2 (1, Ar' = C6H3-2,6{C6H3-2,6- iPr2}2), a rare metal-metal bonded cobalt-tin cluster with low-coordinate tin atoms, was prepared by the reaction of [K(thf)0.2][Co(1,5-cod)2] (cod = 1,5-cyclooctadiene) with [Ar'Sn(µ-Cl)]2. This reaction illustrates a promising synthetic strategy to access uncommon metal clusters. The structure of 1 features a rhomboidal Co2Sn2 core with strong metal-metal bonds between tin and cobalt and a weaker tin-tin interaction. Reaction of 1 with white phosphorus afforded [Ar'2Sn2Co2P4] (2), the first molecular cluster compound containing phosphorus, cobalt and tin.

Reaction of a 2,4,6-triphenylphosphinine ferrate anion with electrophiles: a new route to phosphacyclohexadienyl complexes.

A novel, versatile route to phosphorus- and carbon-substituted η(5)-phosphacyclohexadienyl complexes was developed. Reaction of the anionic 2,4,6-triphenylphosphinine iron complex [K([18]crown-6)(thf)2][Cp*Fe(PC5Ph3H2)] (1) with selected main group element electrophiles afforded the new complexes [Cp*Fe(2-endo-H-PC5Ph3H2)] (endo-3), [Cp*Fe(2-exo-H-PC5Ph3H2)] (exo-3), [Cp*Fe(1-Me-PC5Ph3H2)] (4), [Cp*Fe(1-Me3Si-PC5Ph3H2)] (5), [Cp*Fe(1-PPh2-PC5Ph3H2)] (6) and [Cp*Fe(2-BCat-PC5Ph3H2)] (7, BCat = 2-benzo[d][1,3,2]dioxaborol-2-yl). Initial attack of the electrophile at phosphorus was observed, leading to a P-substitued phosphinine ligand. A subsequent rearragement occured in some cases, resulting in C-substituted phosphinine complexes endo-3, exo-3 and 7. The new complexes were characterized by (1)H, (31)P{(1)H}, and (13)C{(1)H} NMR spectroscopy, UV-vis spectroscopy and elemental analysis; their molecular structures were determined by X-ray crystallography.