Synthesis and reactions of triphenylsilanethiolato complexes of manganese(II), iron(II), cobalt(II), and nickel(II)

Takashi Komuro, Hiroyuki Kawaguchi, Kazuyuki Tatsumi

Research output: Contribution to journalArticlepeer-review

50 Citations (Scopus)

Abstract

Reactions of Fe[N(SiMe3)2]2 with 1 and 2 equiv of Ph3SiSH in hexane afforded dinuclear silanethiolato complexes, [Fe{N(SiMe3)2}(μ-SSiPh3)]2 (1) and [Fe(SSiPh3)(μ-SSiPh3)]2 (2), respectively. Various Lewis bases were readily added to 2, generating mononuclear adducts, Fe(SSiPh3)2(L)2 [L = CH3CN (3a), 4-tBuC5H4N (3b), PEt3 (3c), (LL) = tmeda (3d)]. From the analogous reactions of M[N(SiMe3)2]2 (M = Mn, Co) and [Ni(NPh2)2]2 with Ph3SiSH in the presence of TMEDA, the corresponding silanethiolato complexes, M(SSiPh3)2(tmeda) [M = Mn (4), Co (5), Ni (6)], were isolated. Treatment of 3a with (PPh4)2[MoS4] or (NEt4)2[FeCl4] resulted in formation of a linear trinuclear Fe-Mo-Fe cluster (PPh4)2[MoS4{Fe (SSiPh3)2}2] (7) or a dinuclear complex (NEt4)2[Fe2 (SSiPh3)2Cl4] (8). On the other hand, the reaction of 3a with [Cu(CH3CN)4](PF6) gave a cyclic tetranuclear copper cluster Cu4(SSiPh3)4 (9), where silanethiolato ligands were transferred from iron to copper. Silicon-sulfur bond cleavage was found to occur when the cobalt complex 5 was treated with (NBu4)F in THF, and a cobalt-sulfido cluster Co63-S)8(PPh3)6 (10) was isolated upon addition of PPh3 to the reaction system. The silanethiolato complexes reported here are expected to serve as convenient precursors for sulfido cluster synthesis.

Original languageEnglish
Pages (from-to)5083-5090
Number of pages8
JournalInorganic Chemistry
Volume41
Issue number20
DOIs
Publication statusPublished - 2002 Oct 7
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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