The coordination chemistry of iminooxosulphuranes VI. Factors affecting coordination geometry in complexes of tosyliminooxosulphurane

Max Herberhold; Anthony F. Hill

doi:10.1016/0022-328X(90)85277-6

The coordination chemistry of iminooxosulphuranes VI. Factors affecting coordination geometry in complexes of tosyliminooxosulphurane

Max Herberhold^*
, Anthony F. Hill

^*Corresponding author for this work

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

19 Citations (Scopus)

Abstract

The complexes [ML_n(PPh₃)₂(OSN-SO₂C₆H₄Me-4)] (M = Ru, Rh, Os, Ir) have been prepared from the 16-electron complex [ML_n(PPh₃)₂] or the corresponding tris(phosphine)compounds [ML_n(PPh₃)₃]. The sulphinylamine cumulene adopts one of three possible bonding geometries (pyramidal, or coplanar through sulphur, or π-coordination through sulphur and nitrogen). The preference for a particular mode in a given complex is discussed in terms of metal electron density, d-orbital occupancy, oxidation state and frontier orbital symmetry. Treatment of the complex [RhCl(PPh₃)₂(OSNSO₂C₆H₄Me-4)] (prepared from tosyliminooxosulphurane and [RhCl(PPh₃)₃]) with carbon monoxide results in a rearrangement of the π-bond cumulene in the precursor to a pyramidally bound ligand in the CO adduct [RhCl(CO)(PPh₃)₂(OSN-SO₂C₆H₄Me-4)].

Original language	English
Pages (from-to)	195-206
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	395
Issue number	2
DOIs	https://doi.org/10.1016/0022-328X(90)85277-6
Publication status	Published - 25 Sept 1990
Externally published	Yes

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title = "The coordination chemistry of iminooxosulphuranes VI. Factors affecting coordination geometry in complexes of tosyliminooxosulphurane",

abstract = "The complexes [MLn(PPh3)2(OSN-SO2C6H4Me-4)] (M = Ru, Rh, Os, Ir) have been prepared from the 16-electron complex [MLn(PPh3)2] or the corresponding tris(phosphine)compounds [MLn(PPh3)3]. The sulphinylamine cumulene adopts one of three possible bonding geometries (pyramidal, or coplanar through sulphur, or π-coordination through sulphur and nitrogen). The preference for a particular mode in a given complex is discussed in terms of metal electron density, d-orbital occupancy, oxidation state and frontier orbital symmetry. Treatment of the complex [RhCl(PPh3)2(OSNSO2C6H4Me-4)] (prepared from tosyliminooxosulphurane and [RhCl(PPh3)3]) with carbon monoxide results in a rearrangement of the π-bond cumulene in the precursor to a pyramidally bound ligand in the CO adduct [RhCl(CO)(PPh3)2(OSN-SO2C6H4Me-4)].",

author = "Max Herberhold and Hill, \{Anthony F.\}",

year = "1990",

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doi = "10.1016/0022-328X(90)85277-6",

language = "English",

volume = "395",

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journal = "Journal of Organometallic Chemistry",

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T1 - The coordination chemistry of iminooxosulphuranes VI. Factors affecting coordination geometry in complexes of tosyliminooxosulphurane

AU - Herberhold, Max

AU - Hill, Anthony F.

PY - 1990/9/25

Y1 - 1990/9/25

N2 - The complexes [MLn(PPh3)2(OSN-SO2C6H4Me-4)] (M = Ru, Rh, Os, Ir) have been prepared from the 16-electron complex [MLn(PPh3)2] or the corresponding tris(phosphine)compounds [MLn(PPh3)3]. The sulphinylamine cumulene adopts one of three possible bonding geometries (pyramidal, or coplanar through sulphur, or π-coordination through sulphur and nitrogen). The preference for a particular mode in a given complex is discussed in terms of metal electron density, d-orbital occupancy, oxidation state and frontier orbital symmetry. Treatment of the complex [RhCl(PPh3)2(OSNSO2C6H4Me-4)] (prepared from tosyliminooxosulphurane and [RhCl(PPh3)3]) with carbon monoxide results in a rearrangement of the π-bond cumulene in the precursor to a pyramidally bound ligand in the CO adduct [RhCl(CO)(PPh3)2(OSN-SO2C6H4Me-4)].

AB - The complexes [MLn(PPh3)2(OSN-SO2C6H4Me-4)] (M = Ru, Rh, Os, Ir) have been prepared from the 16-electron complex [MLn(PPh3)2] or the corresponding tris(phosphine)compounds [MLn(PPh3)3]. The sulphinylamine cumulene adopts one of three possible bonding geometries (pyramidal, or coplanar through sulphur, or π-coordination through sulphur and nitrogen). The preference for a particular mode in a given complex is discussed in terms of metal electron density, d-orbital occupancy, oxidation state and frontier orbital symmetry. Treatment of the complex [RhCl(PPh3)2(OSNSO2C6H4Me-4)] (prepared from tosyliminooxosulphurane and [RhCl(PPh3)3]) with carbon monoxide results in a rearrangement of the π-bond cumulene in the precursor to a pyramidally bound ligand in the CO adduct [RhCl(CO)(PPh3)2(OSN-SO2C6H4Me-4)].

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The coordination chemistry of iminooxosulphuranes VI. Factors affecting coordination geometry in complexes of tosyliminooxosulphurane

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