Preparation, crystal structures, and behavior in solution of cobalt(III) complexes containing 2-cyanoethylphosphines: Trans-[Co(Me 2dtc) 2{P(CH 2CH 2CN) nPh 3-n}] BF 4 (n = 1-3; Me 2dtc-: N,N-dimethyldithiocarbamate)

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

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A series of cobalt(III) complexes containing 2-cyanoethylphosphines, [Co(Me 2dtc) 2{P(CH 2CH 2CN) nPh 3-n} 2]BF 4{Me 2dtc -: 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 CoP bond lengths for the 2-cyanoethylphosphines in complexes 13 are almost invariant to the number of 2-cyanoethyl substituent groups. Unlike related complexes with other monodentate P-donor ligands, complexes 13 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 weakσ-donor and π-acceptor abilities of 2-cyanoethylphosphines. Furthermore, mixing of complex 1 and NaN 3 in acetonitrile gave cis- [Co(Me 2dtc) 2(N 3){P(CH 2CH 2CN)Ph 2}] quantitatively, and refluxing the mixture resulted in the phosphine-tetrazolate complex, [Co(Me 2dtc) 2(Ph 2PCH 2CH 2CN 4- κ 2P,N 1)] (4).

Original languageEnglish
Pages (from-to)1160-1166
Number of pages7
JournalBulletin of the Chemical Society of Japan
Issue number10
Publication statusPublished - Oct 29 2012


ASJC Scopus subject areas

  • Chemistry(all)

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