Preparation, Crystal Structures, and Behavior in Solution of Cobalt(III) Complexes Containing 2-Cyanoethylphosphines: trans-[Co(Me2dtc)2{P(CH2CH2CN)nPh3−n}]BF4 (n = 1–3; Me2dtc−: N,N-Dimethyldithiocarbamate)

Keiko Kihara, Takayoshi Suzuki, Masakazu Kita, Yukinari Sunatsuki, Masaaki Kojima, Hideo D Takagi

doi:10.1246/bcsj.20120148

<jats:title>Abstract</jats:title> <jats:p>A series of cobalt(III) complexes containing 2-cyanoethylphosphines, [Co(Me2dtc)2{P(CH2CH2CN)nPh3−n}2]BF4 {Me2dtc−: N,N-dimethyldithiocarbamate; n = 1 (1), 2 (2), and 3 (3)} have been prepared, and their molecular structures in the crystals and in solution have been characterized. X-ray analysis revealed that all complexes isolated as single-crystals were the trans-isomers. The Co–P bond lengths for the 2-cyanoethylphosphines in complexes 1–3 are almost invariant to the number of 2-cyanoethyl substituent groups. Unlike related complexes with other monodentate P-donor ligands, complexes 1–3 in solution showed dissociation and isomerization equilibriums, which were achieved immediately after dissolving the crystals. These characteristic features of the complexes would result from the weak σ-donor and π-acceptor abilities of 2-cyanoethylphosphines. Furthermore, mixing of complex 1 and NaN3 in acetonitrile gave cis-[Co(Me2dtc)2(N3){P(CH2CH2CN)Ph2}] quantitatively, and refluxing the mixture resulted in the phosphine–tetrazolate complex, [Co(Me2dtc)2(Ph2PCH2CH2CN4-κ2P,N1)] (4).</jats:p>

Preparation, Crystal Structures, and Behavior in Solution of Cobalt(III) Complexes Containing 2-Cyanoethylphosphines: <i>trans</i>-[Co(Me2dtc)2{P(CH2CH2CN)<i>n</i>Ph3−<i>n</i>}]BF4 (<i>n</i> = 1–3; Me2dtc−: <i>N</i>,<i>N</i>-Dimethyldithiocarbamate)

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