Competition between NH and CH activation in the thermolysis of Os3(CO)11[NHC(CH)2)5]. The molecular structure of Os3(CO)9(μ2-H)2- [μ3-NHC(CH)24C]

Georg Süss-Fink; Paul R. Raithby

doi:10.1016/S0020-1693(00)83646-4

Competition between NH and CH activation in the thermolysis of Os₃(CO)₁₁[NHC(CH)₂)₅]. The molecular structure of Os₃(CO)₉(μ₂-H)_2- [μ₃-NHC(CH)₂₄C]

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Abstract

When the trinuclear cyclohexylideneimine complex OS₃(CO)₁₁[NHC(CH₂)₅] is heated in refluxing hydrocarbons, a competition between NH and C-H activation is observed. Upon cleavage of the NH bond, hydrogen transfer onto the metal framework occurs and the cluster OS₃(CO)₁₀(μ₂-H)(μ₂-NC- (CH)₂)₅] is formed. An alternative product, OS₃- (CO)₉(μ-H)₂[μ₃-NHC(CH)₂)₄C], is formed from the cleavage of two CH bonds and hydrogen transfer onto the OS₃ triangle. Crystals of OS₃(CO)₉(μ₂-H)₂- [μ₃-NHC(CH)₂)₄C] are monoclinic, space group P2₁/c, with Z = 4 and cell dimensions a = 9.479(4), b = 13.498(5), c= 15.943(7) Å, β = 92.55(3)°. The structure has been solved from diffractometer data by a combination of direct methods and Fourier difference techniques and refined by blocked-cascade least-squares to R = 0.042 for 2882 independent observed reflections. The three Os atoms define an isosceles triangle one edge of which is bridged by a carbon atoms of the six-membered ring. The third Os atom is coordinated to the nitrogen atom, in such a way that the NHC(CH)₂)₄C moiety caps one side of the triangle.

Original language	English
Pages (from-to)	109-114
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	71
Issue number	C
DOIs	https://doi.org/10.1016/S0020-1693(00)83646-4
Publication status	Published - 31 Dec 1983

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0020-1693(00)83646-4

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@article{4c9662ccb55746d2806da70f780f8275,

title = "Competition between NH and CH activation in the thermolysis of Os3(CO)11[NHC(CH)2)5]. The molecular structure of Os3(CO)9(μ2-H)2- [μ3-NHC(CH)24C]",

abstract = "When the trinuclear cyclohexylideneimine complex OS3(CO)11[NHC(CH2)5] is heated in refluxing hydrocarbons, a competition between NH and C-H activation is observed. Upon cleavage of the NH bond, hydrogen transfer onto the metal framework occurs and the cluster OS3(CO)10(μ2-H)(μ2-NC- (CH)2)5] is formed. An alternative product, OS3- (CO)9(μ-H)2[μ3-NHC(CH)2)4C], is formed from the cleavage of two CH bonds and hydrogen transfer onto the OS3 triangle. Crystals of OS3(CO)9(μ2-H)2- [μ3-NHC(CH)2)4C] are monoclinic, space group P21/c, with Z = 4 and cell dimensions a = 9.479(4), b = 13.498(5), c= 15.943(7) {\AA}, β = 92.55(3)°. The structure has been solved from diffractometer data by a combination of direct methods and Fourier difference techniques and refined by blocked-cascade least-squares to R = 0.042 for 2882 independent observed reflections. The three Os atoms define an isosceles triangle one edge of which is bridged by a carbon atoms of the six-membered ring. The third Os atom is coordinated to the nitrogen atom, in such a way that the NHC(CH)2)4C moiety caps one side of the triangle.",

author = "Georg S{\"u}ss-Fink and Raithby, \{Paul R.\}",

year = "1983",

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doi = "10.1016/S0020-1693(00)83646-4",

language = "English",

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journal = "Inorganica Chimica Acta",

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T1 - Competition between NH and CH activation in the thermolysis of Os3(CO)11[NHC(CH)2)5]. The molecular structure of Os3(CO)9(μ2-H)2- [μ3-NHC(CH)24C]

AU - Süss-Fink, Georg

AU - Raithby, Paul R.

PY - 1983/12/31

Y1 - 1983/12/31

N2 - When the trinuclear cyclohexylideneimine complex OS3(CO)11[NHC(CH2)5] is heated in refluxing hydrocarbons, a competition between NH and C-H activation is observed. Upon cleavage of the NH bond, hydrogen transfer onto the metal framework occurs and the cluster OS3(CO)10(μ2-H)(μ2-NC- (CH)2)5] is formed. An alternative product, OS3- (CO)9(μ-H)2[μ3-NHC(CH)2)4C], is formed from the cleavage of two CH bonds and hydrogen transfer onto the OS3 triangle. Crystals of OS3(CO)9(μ2-H)2- [μ3-NHC(CH)2)4C] are monoclinic, space group P21/c, with Z = 4 and cell dimensions a = 9.479(4), b = 13.498(5), c= 15.943(7) Å, β = 92.55(3)°. The structure has been solved from diffractometer data by a combination of direct methods and Fourier difference techniques and refined by blocked-cascade least-squares to R = 0.042 for 2882 independent observed reflections. The three Os atoms define an isosceles triangle one edge of which is bridged by a carbon atoms of the six-membered ring. The third Os atom is coordinated to the nitrogen atom, in such a way that the NHC(CH)2)4C moiety caps one side of the triangle.

AB - When the trinuclear cyclohexylideneimine complex OS3(CO)11[NHC(CH2)5] is heated in refluxing hydrocarbons, a competition between NH and C-H activation is observed. Upon cleavage of the NH bond, hydrogen transfer onto the metal framework occurs and the cluster OS3(CO)10(μ2-H)(μ2-NC- (CH)2)5] is formed. An alternative product, OS3- (CO)9(μ-H)2[μ3-NHC(CH)2)4C], is formed from the cleavage of two CH bonds and hydrogen transfer onto the OS3 triangle. Crystals of OS3(CO)9(μ2-H)2- [μ3-NHC(CH)2)4C] are monoclinic, space group P21/c, with Z = 4 and cell dimensions a = 9.479(4), b = 13.498(5), c= 15.943(7) Å, β = 92.55(3)°. The structure has been solved from diffractometer data by a combination of direct methods and Fourier difference techniques and refined by blocked-cascade least-squares to R = 0.042 for 2882 independent observed reflections. The three Os atoms define an isosceles triangle one edge of which is bridged by a carbon atoms of the six-membered ring. The third Os atom is coordinated to the nitrogen atom, in such a way that the NHC(CH)2)4C moiety caps one side of the triangle.

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DO - 10.1016/S0020-1693(00)83646-4

M3 - Article

AN - SCOPUS:13244258973

SN - 0020-1693

VL - 71

SP - 109

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JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - C

ER -

Competition between NH and CH activation in the thermolysis of Os₃(CO)₁₁[NHC(CH)₂)₅]. The molecular structure of Os₃(CO)₉(μ₂-H)_2- [μ₃-NHC(CH)₂₄C]

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