Three-coordinate bis(phosphinimino)methanide derivatives of 'open shell' [M(II)] (M = Mn, Fe, Co) transition metals

Michael S. Hill; Peter B. Hitchcock

doi:10.1016/j.jorganchem.2004.06.050

Three-coordinate bis(phosphinimino)methanide derivatives of 'open shell' [M(II)] (M = Mn, Fe, Co) transition metals

Michael S. Hill, Peter B. Hitchcock

Research output: Contribution to journal › Article › peer-review

1 Citation (SciVal)

Abstract

An alternative two-step synthesis of the previously reported bis(diphenylphosphinimino)methane [CH₂(Ph₂P = NC₆H₃ⁱPr₂-2.6)₂] involving bromine oxidation of dppm and metathesis with 2,6-diisopropylaniline is described. [CH₂(Ph₂P NC₆H₃ⁱPr₂-2,6)₂] is readily deprotonated by the transition metal silylamides [M{N(SiMe₃)₂}₂] (M = Mn, Fe and Co) to provide a series of exclusively three-coordinate derivatives [{CH(Ph₂PNC₆H₃ⁱ Pr₂-2,6)₂M{N(SiMe₃)₂}] which have been characterised by elemental analysis, magnetic measurements and, in the case of the Fe derivative, X-ray structural analysis. Reactivity studies have shown that even such sterically demanding bis(phosphinimino)methanide ligands are prone to protonolysis and reductive [P(V) to P(III)] degradation which limits their utility as stable platforms for further M(II) derivitisation.

Original language	English
Pages (from-to)	3163-3167
Number of pages	5
Journal	Journal of Organometallic Chemistry
Volume	689
Issue number	20
DOIs	https://doi.org/10.1016/j.jorganchem.2004.06.050
Publication status	Published - 29 Sep 2004

Keywords

Amides
Cobalt
Iron
Manganese
Three-coordinate

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.jorganchem.2004.06.050

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title = "Three-coordinate bis(phosphinimino)methanide derivatives of 'open shell' [M(II)] (M = Mn, Fe, Co) transition metals",

abstract = "An alternative two-step synthesis of the previously reported bis(diphenylphosphinimino)methane [CH2(Ph2P = NC6H3iPr2-2.6)2] involving bromine oxidation of dppm and metathesis with 2,6-diisopropylaniline is described. [CH2(Ph2P NC6H3iPr2-2,6)2] is readily deprotonated by the transition metal silylamides [M{N(SiMe3)2}2] (M = Mn, Fe and Co) to provide a series of exclusively three-coordinate derivatives [{CH(Ph2PNC6H3i Pr2-2,6)2M{N(SiMe3)2}] which have been characterised by elemental analysis, magnetic measurements and, in the case of the Fe derivative, X-ray structural analysis. Reactivity studies have shown that even such sterically demanding bis(phosphinimino)methanide ligands are prone to protonolysis and reductive [P(V) to P(III)] degradation which limits their utility as stable platforms for further M(II) derivitisation.",

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author = "Hill, {Michael S.} and Hitchcock, {Peter B.}",

year = "2004",

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doi = "10.1016/j.jorganchem.2004.06.050",

language = "English",

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AU - Hill, Michael S.

AU - Hitchcock, Peter B.

PY - 2004/9/29

Y1 - 2004/9/29

N2 - An alternative two-step synthesis of the previously reported bis(diphenylphosphinimino)methane [CH2(Ph2P = NC6H3iPr2-2.6)2] involving bromine oxidation of dppm and metathesis with 2,6-diisopropylaniline is described. [CH2(Ph2P NC6H3iPr2-2,6)2] is readily deprotonated by the transition metal silylamides [M{N(SiMe3)2}2] (M = Mn, Fe and Co) to provide a series of exclusively three-coordinate derivatives [{CH(Ph2PNC6H3i Pr2-2,6)2M{N(SiMe3)2}] which have been characterised by elemental analysis, magnetic measurements and, in the case of the Fe derivative, X-ray structural analysis. Reactivity studies have shown that even such sterically demanding bis(phosphinimino)methanide ligands are prone to protonolysis and reductive [P(V) to P(III)] degradation which limits their utility as stable platforms for further M(II) derivitisation.

AB - An alternative two-step synthesis of the previously reported bis(diphenylphosphinimino)methane [CH2(Ph2P = NC6H3iPr2-2.6)2] involving bromine oxidation of dppm and metathesis with 2,6-diisopropylaniline is described. [CH2(Ph2P NC6H3iPr2-2,6)2] is readily deprotonated by the transition metal silylamides [M{N(SiMe3)2}2] (M = Mn, Fe and Co) to provide a series of exclusively three-coordinate derivatives [{CH(Ph2PNC6H3i Pr2-2,6)2M{N(SiMe3)2}] which have been characterised by elemental analysis, magnetic measurements and, in the case of the Fe derivative, X-ray structural analysis. Reactivity studies have shown that even such sterically demanding bis(phosphinimino)methanide ligands are prone to protonolysis and reductive [P(V) to P(III)] degradation which limits their utility as stable platforms for further M(II) derivitisation.

KW - Amides

KW - Cobalt

KW - Iron

KW - Manganese

KW - Three-coordinate

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JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

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IS - 20

ER -

Three-coordinate bis(phosphinimino)methanide derivatives of 'open shell' [M(II)] (M = Mn, Fe, Co) transition metals

Abstract

Keywords

ASJC Scopus subject areas

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