Thermolysis of the osmium-antimony clusters Os3(CO) 11(SbMe2Ar): Higher nuclearity clusters and arrested ortho metalation

Kiat Hwa Chan; Weng Kee Leong; Kar Hang Garvin Mak

doi:10.1021/om0508132

Thermolysis of the osmium-antimony clusters Os₃(CO) ₁₁(SbMe₂Ar): Higher nuclearity clusters and arrested ortho metalation

Kiat Hwa Chan, Weng Kee Leong^*, Kar Hang Garvin Mak

^*Corresponding author for this work

National University of Singapore

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

24 Citations (Scopus)

Abstract

Thermolysis of the clusters Os₃(CO)₁₁(SbMe ₂Ar) (1, where Ar = Ph (b), o-tolyl (c), p-tolyl (d)), in refluxing octane gave the clusters Os₃(μ-SbMe₂)(μ-H) (μ₃η²-C₆H₃R)(CO)₉ (2, where R = H (b), Me (c)), in good yields; both tolyl derivatives gave the same 4-substituted phenylene cluster. Among the minor products also isolated from the thermolysis of 1b were the higher nuclearity clusters Os ₆(μ₃-SbMe)-(μ₃,η²-C ₆H₄)(CO)₂₀ (4) and Os₆(μ ₄-Sb)(μ₄-Sb)(μ-SbMe₂)(μ-H) (μ₃,η²-C₆H₄) ₂(CH₃)(CO)₁₆ (5), which contains an Os-CH ₃ moiety. Thermolysis of the 3,5-xylyl analogue Os ₃(CO)₁₁{SbMe₂(3,5-Me₂C ₆H₃)} (1f), on the other hand, gave the unusual species Os₃(μ-SbMe₂)(μ₃,η¹: η²:η²- C₆H₃Me ₂)(CO)₉(6), in which ortho metalation of the xylyl ring has apparently been arrested.

Original language	English
Pages (from-to)	250-259
Number of pages	10
Journal	Organometallics
Volume	25
Issue number	1
DOIs	https://doi.org/10.1021/om0508132
Publication status	Published - Jan 2 2006
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Thermolysis of the osmium-antimony clusters Os3(CO) 11(SbMe2Ar): Higher nuclearity clusters and arrested ortho metalation",

abstract = "Thermolysis of the clusters Os3(CO)11(SbMe 2Ar) (1, where Ar = Ph (b), o-tolyl (c), p-tolyl (d)), in refluxing octane gave the clusters Os3(μ-SbMe2)(μ-H) (μ3η2-C6H3R)(CO)9 (2, where R = H (b), Me (c)), in good yields; both tolyl derivatives gave the same 4-substituted phenylene cluster. Among the minor products also isolated from the thermolysis of 1b were the higher nuclearity clusters Os 6(μ3-SbMe)-(μ3,η2-C 6H4)(CO)20 (4) and Os6(μ 4-Sb)(μ4-Sb)(μ-SbMe2)(μ-H) (μ3,η2-C6H4) 2(CH3)(CO)16 (5), which contains an Os-CH 3 moiety. Thermolysis of the 3,5-xylyl analogue Os 3(CO)11{SbMe2(3,5-Me2C 6H3)} (1f), on the other hand, gave the unusual species Os3(μ-SbMe2)(μ3,η1: η2:η2- C6H3Me 2)(CO)9(6), in which ortho metalation of the xylyl ring has apparently been arrested.",

author = "Chan, {Kiat Hwa} and Leong, {Weng Kee} and Mak, {Kar Hang Garvin}",

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AU - Leong, Weng Kee

AU - Mak, Kar Hang Garvin

PY - 2006/1/2

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N2 - Thermolysis of the clusters Os3(CO)11(SbMe 2Ar) (1, where Ar = Ph (b), o-tolyl (c), p-tolyl (d)), in refluxing octane gave the clusters Os3(μ-SbMe2)(μ-H) (μ3η2-C6H3R)(CO)9 (2, where R = H (b), Me (c)), in good yields; both tolyl derivatives gave the same 4-substituted phenylene cluster. Among the minor products also isolated from the thermolysis of 1b were the higher nuclearity clusters Os 6(μ3-SbMe)-(μ3,η2-C 6H4)(CO)20 (4) and Os6(μ 4-Sb)(μ4-Sb)(μ-SbMe2)(μ-H) (μ3,η2-C6H4) 2(CH3)(CO)16 (5), which contains an Os-CH 3 moiety. Thermolysis of the 3,5-xylyl analogue Os 3(CO)11{SbMe2(3,5-Me2C 6H3)} (1f), on the other hand, gave the unusual species Os3(μ-SbMe2)(μ3,η1: η2:η2- C6H3Me 2)(CO)9(6), in which ortho metalation of the xylyl ring has apparently been arrested.

AB - Thermolysis of the clusters Os3(CO)11(SbMe 2Ar) (1, where Ar = Ph (b), o-tolyl (c), p-tolyl (d)), in refluxing octane gave the clusters Os3(μ-SbMe2)(μ-H) (μ3η2-C6H3R)(CO)9 (2, where R = H (b), Me (c)), in good yields; both tolyl derivatives gave the same 4-substituted phenylene cluster. Among the minor products also isolated from the thermolysis of 1b were the higher nuclearity clusters Os 6(μ3-SbMe)-(μ3,η2-C 6H4)(CO)20 (4) and Os6(μ 4-Sb)(μ4-Sb)(μ-SbMe2)(μ-H) (μ3,η2-C6H4) 2(CH3)(CO)16 (5), which contains an Os-CH 3 moiety. Thermolysis of the 3,5-xylyl analogue Os 3(CO)11{SbMe2(3,5-Me2C 6H3)} (1f), on the other hand, gave the unusual species Os3(μ-SbMe2)(μ3,η1: η2:η2- C6H3Me 2)(CO)9(6), in which ortho metalation of the xylyl ring has apparently been arrested.

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Thermolysis of the osmium-antimony clusters Os₃(CO) ₁₁(SbMe₂Ar): Higher nuclearity clusters and arrested ortho metalation

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