Issue 9, 2001

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

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) Å in 5 to 2.303(9) Å 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).

Graphical abstract: Cyanide-bridged complexes with Sn(II)Mn(I), Sn(II)Mn(II), Sn(IV)Mn(I) and Sn(IV)Mn(II) oxidation states [ ]

Supplementary files

Article information

Article type
Paper
Submitted
19 Jan 2001
Accepted
15 Mar 2001
First published
17 Apr 2001

J. Chem. Soc., Dalton Trans., 2001, 1421-1427

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

K. M. Anderson, N. G. Connelly, N. J. Goodwin, G. R. Lewis, M. T. Moreno, A. G. Orpen and A. J. Wood, J. Chem. Soc., Dalton Trans., 2001, 1421 DOI: 10.1039/B100721L

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