The ditertiary-phosphane-bridged heteronuclear cluster RuOs 3(μ-H)2(CO)9(μ-CO)2(μ-dppm): Synthesis and reactivity with alkynes

Yong Leng Kelvin Tan; Kee Leong Weng

doi:10.1002/ejic.200601118

The ditertiary-phosphane-bridged heteronuclear cluster RuOs ₃(μ-H)₂(CO)₉(μ-CO)₂(μ-dppm): Synthesis and reactivity with alkynes

Yong Leng Kelvin Tan, Kee Leong Weng^*

^*Corresponding author for this work

National University of Singapore

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

2 Citations (Scopus)

Abstract

A high-yielding alternative synthesis of the dppm-bridged heteronuclear cluster RuOs₃(μ-H)₂(CO)₉(μ-CO) ₂(μ-dppm) (1) [dppm = bis(diphenylphosphanyl)methane] has been developed. Thermolysis of 1 resulted in dephenylation of both phosphane groups to afford the butterfly cluster RuOs₃(CO)₁₂(μ ⁴,κ²:κ²-PhPCH₂PPh) (2). The reaction of 1 with selected alkynes afforded the products RuOs ₃(μ-H)(CO)₈(μCO)(μ₃, κ²:κ¹-PhPCH₂PPh₂) (μ₃η¹:η²:η¹-L) (3) (L = alkyne) in which the alkyne is aligned parallel to an Os-Os bond (// Os-Os isomer). The clusters incorporating internal alkynes underwent isomerization to the //Ru-Os isomer by alkyne and hydride migration. Several other cluster products of these reactions were also identified, including RuOs ₃(μ-H)-(CO)₈(μ-CO)(μ₃, κ²:K¹-PhPCH₂PPh₂) (μ₃,η¹:η²:η¹- tBuC₂CHO) (6) in which the methyl group of the alkyne has been oxidized to an aldehyde.

Original language	English
Pages (from-to)	1585-1598
Number of pages	14
Journal	European Journal of Inorganic Chemistry
Issue number	11
DOIs	https://doi.org/10.1002/ejic.200601118
Publication status	Published - 2007
Externally published	Yes

ASJC Scopus Subject Areas

Inorganic Chemistry

Keywords

Alkynes
Ditertiary phosphanes
Heterometallic complexes
Osmium
Ruthenium

Access to Document

10.1002/ejic.200601118

Cite this

@article{3ba1b6590332489cb2df47b45aacd4a6,

title = "The ditertiary-phosphane-bridged heteronuclear cluster RuOs 3(μ-H)2(CO)9(μ-CO)2(μ-dppm): Synthesis and reactivity with alkynes",

abstract = "A high-yielding alternative synthesis of the dppm-bridged heteronuclear cluster RuOs3(μ-H)2(CO)9(μ-CO) 2(μ-dppm) (1) [dppm = bis(diphenylphosphanyl)methane] has been developed. Thermolysis of 1 resulted in dephenylation of both phosphane groups to afford the butterfly cluster RuOs3(CO)12(μ 4,κ2:κ2-PhPCH2PPh) (2). The reaction of 1 with selected alkynes afforded the products RuOs 3(μ-H)(CO)8(μCO)(μ3, κ2:κ1-PhPCH2PPh2) (μ3η1:η2:η1-L) (3) (L = alkyne) in which the alkyne is aligned parallel to an Os-Os bond (// Os-Os isomer). The clusters incorporating internal alkynes underwent isomerization to the //Ru-Os isomer by alkyne and hydride migration. Several other cluster products of these reactions were also identified, including RuOs 3(μ-H)-(CO)8(μ-CO)(μ3, κ2:K1-PhPCH2PPh2) (μ3,η1:η2:η1- tBuC2CHO) (6) in which the methyl group of the alkyne has been oxidized to an aldehyde.",

keywords = "Alkynes, Ditertiary phosphanes, Heterometallic complexes, Osmium, Ruthenium",

author = "Tan, {Yong Leng Kelvin} and Weng, {Kee Leong}",

year = "2007",

doi = "10.1002/ejic.200601118",

language = "English",

pages = "1585--1598",

journal = "European Journal of Inorganic Chemistry",

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publisher = "John Wiley and Sons Ltd",

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TY - JOUR

T1 - The ditertiary-phosphane-bridged heteronuclear cluster RuOs 3(μ-H)2(CO)9(μ-CO)2(μ-dppm)

T2 - Synthesis and reactivity with alkynes

AU - Tan, Yong Leng Kelvin

AU - Weng, Kee Leong

PY - 2007

Y1 - 2007

N2 - A high-yielding alternative synthesis of the dppm-bridged heteronuclear cluster RuOs3(μ-H)2(CO)9(μ-CO) 2(μ-dppm) (1) [dppm = bis(diphenylphosphanyl)methane] has been developed. Thermolysis of 1 resulted in dephenylation of both phosphane groups to afford the butterfly cluster RuOs3(CO)12(μ 4,κ2:κ2-PhPCH2PPh) (2). The reaction of 1 with selected alkynes afforded the products RuOs 3(μ-H)(CO)8(μCO)(μ3, κ2:κ1-PhPCH2PPh2) (μ3η1:η2:η1-L) (3) (L = alkyne) in which the alkyne is aligned parallel to an Os-Os bond (// Os-Os isomer). The clusters incorporating internal alkynes underwent isomerization to the //Ru-Os isomer by alkyne and hydride migration. Several other cluster products of these reactions were also identified, including RuOs 3(μ-H)-(CO)8(μ-CO)(μ3, κ2:K1-PhPCH2PPh2) (μ3,η1:η2:η1- tBuC2CHO) (6) in which the methyl group of the alkyne has been oxidized to an aldehyde.

AB - A high-yielding alternative synthesis of the dppm-bridged heteronuclear cluster RuOs3(μ-H)2(CO)9(μ-CO) 2(μ-dppm) (1) [dppm = bis(diphenylphosphanyl)methane] has been developed. Thermolysis of 1 resulted in dephenylation of both phosphane groups to afford the butterfly cluster RuOs3(CO)12(μ 4,κ2:κ2-PhPCH2PPh) (2). The reaction of 1 with selected alkynes afforded the products RuOs 3(μ-H)(CO)8(μCO)(μ3, κ2:κ1-PhPCH2PPh2) (μ3η1:η2:η1-L) (3) (L = alkyne) in which the alkyne is aligned parallel to an Os-Os bond (// Os-Os isomer). The clusters incorporating internal alkynes underwent isomerization to the //Ru-Os isomer by alkyne and hydride migration. Several other cluster products of these reactions were also identified, including RuOs 3(μ-H)-(CO)8(μ-CO)(μ3, κ2:K1-PhPCH2PPh2) (μ3,η1:η2:η1- tBuC2CHO) (6) in which the methyl group of the alkyne has been oxidized to an aldehyde.

KW - Alkynes

KW - Ditertiary phosphanes

KW - Heterometallic complexes

KW - Osmium

KW - Ruthenium

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