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Cyanide-bridged complexes with Sn(II)Mn(I), Sn(II)Mn(II), Sn(IV)Mn(I) and Sn(IV)Mn(II) oxidation states †

Authors :
Kirsty M. Anderson
Neil G. Connelly
Maria Teresa Moreno
A. Guy Orpen
Andrew J. Wood
Nicholas J. Goodwin
Gareth R. Lewis
Source :
RIUR: Repositorio Institucional de la Universidad de La Rioja, Universidad de La Rioja (UR), Scopus-Elsevier, RIUR. Repositorio Institucional de la Universidad de La Rioja, instname
Publication Year :
2001
Publisher :
Royal Society of Chemistry (RSC), 2001.

Abstract

The redox-active cyanomanganese carbonyl ligands trans- and cis-[Mn(CN)(CO)2(PR3)(dppm)] (R = OEt or OPh, dppm = Ph2PCH2PPh2) and trans-[Mn(CN)(CO)(dppm)2] react with SnCl2 to give [Cl2SnII(μ-NC)MnILx] [Lx = trans- and cis-(CO)2(PR3)(dppm), R = OEt or OPh, 1–4, and trans-(CO)(dppm)25]; complex 5 is oxidised by [Fe(η-C5H5)2][PF6] to give [Cl2SnII(μ-NC)MnII(CO)(dppm)2][PF6] 5+[PF6]−. X-Ray structural studies on the redox related pair 5 and 5+ are consistent with oxidation localised mainly at Mn although the SnII–NC distance increases from 2.198(3) A in 5 to 2.303(9) A in 5+. The dicarbonyl cyanomanganese ligands react with SnCl4 to give trinuclear trans-[Cl4Sn{(μ-NC)MnLx}2] [Lx = trans- and cis-(CO)2(PR3)(dppm), R = OEt or OPh, 6–9], X-ray studies on 7 showing octahedral geometry at Sn(IV). The reaction of cis-[Mn(CN)(CO)2{P(OEt)3}(dppm)] with one equivalent each of SnCl4 and PPh3 and of trans-[Mn(CN)(CO)(dppm)2] with one equivalent each of SnCl4 and [N(PPh3)2]Cl gives heterobinuclear [Cl4(Ph3P)SnIV(μ-NC)MnI(CO)2{P(OEt)3}(dppm)-cis] 10 and [N(PPh3)2][Cl5SnIV(μ-NC)MnI(CO)(dppm)2-trans], [N(PPh3)2]+(11−), respectively; the latter is oxidised with [Fe(η-C5H5)2][PF6] to give [Cl5SnIV(μ-NC)MnII(CO)(dppm)2-trans] 11, completing a series of cyanide-bridged complexes with core oxidation states Sn(II)Mn(I), Sn(II)Mn(II), Sn(IV)Mn(I) and Sn(IV)Mn(II).

Details

ISSN :
13645447 and 14727773
Database :
OpenAIRE
Journal :
Journal of the Chemical Society, Dalton Transactions
Accession number :
edsair.doi.dedup.....5e200384d1380f7981ec898e5d230972
Full Text :
https://doi.org/10.1039/b100721l