Mo and W dihalide complexes with uncommon trigonal-prismatic geometry imposed by the linear tetraphosphine ancillary ligand and their reactivities toward diazoalkanes

Hidetake Seino; Daisuke Watanabe; Takeshi Ohnishi; Chirima Arita; Yasushi Mizobe

doi:10.1021/ic700371b

Mo and W dihalide complexes with uncommon trigonal-prismatic geometry imposed by the linear tetraphosphine ancillary ligand and their reactivities toward diazoalkanes

Inorg Chem. 2007 Jun 11;46(12):4784-6. doi: 10.1021/ic700371b. Epub 2007 May 10.

Authors

Hidetake Seino¹, Daisuke Watanabe, Takeshi Ohnishi, Chirima Arita, Yasushi Mizobe

Affiliation

¹ Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan.

PMID: 17489589
DOI: 10.1021/ic700371b

Abstract

New Mo and W tetraphosphine-dihalide complexes [MX2(kappa4-P4)] (2, MX=MoCl, MoBr, WBr; P4=meso-o-C6H4(PPhCH2CH2PPh2)2) with uncommon trigonal-prismatic geometries have been prepared. Treatment of ethyl diazoacetate with 2 (MX=MoCl) resulted in catalytic carbenoid-group coupling to give diethyl maleate and fumarate, whereas reactions of 2 with trimethylsilyldiazoalkane formed the diazoalkane complexes trans-[MX(NN=CHSiMe3)-(kappa4-P4)]+ (3+) and cis,mer-[MoCl2(NN=CHSiMe3)(kappa3-P4)]. The molecular structures of 2 (MX=MoCl) and 3[PF6] (MX=WBr) were crystallographically determined.