Substitution of [Ru10C2(CO)24]2- with allene. Reversible formation of [Ru10C2(CO)22(μ-η2:η 2-C3H4)]2- and [Ru10C2(CO)20(μ-η2

Kwangyeol Lee; John R. Shapley

doi:10.1021/om980486g

Substitution of [Ru₁₀C₂(CO)₂₄]^2- with allene. Reversible formation of [Ru₁₀C₂(CO)₂₂(μ-η²:η ²-C₃H₄)]^2- and [Ru₁₀C₂(CO)₂₀(μ-η²

Kwangyeol Lee, John R. Shapley

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

14 Citations (Scopus)

Abstract

Substitution of carbonyl ligands in [Ru₁₀C₂(CO)₂₄]^2- (1) by allene (1,2-propadiene) proceeds cleanly in diglyme at 90°C (1 atm) to afford the monoallene derivative [Ru₁₀C₂(CO)₂₂(μ-η²: η²-C₃H₄)]^2- (2). Treatment of either 1 or 2 with allene at 140°C (1 atm) forms the disubstituted derivative [Ru₁₀C₂(CO)₂₀(μ-η²:η ²-C₃H₄)₂]^2- (3) in high yield. The new clusters have been isolated as salts with [PPN]⁺ or [PPh₃CH₂CH₂PPh₃]²⁺ counterions and have been characterized by analytical, spectroscopic, and X-ray crystallographic methods. The framework structures of both molecular cluster anions 2 and 3 are based on edge-shared bioctahedra, with the allene ligands bridging one or two pairs of apical positions, respectively. The idealized symmetries are C₂ for 2 and D₂ for 3. The solution structures and dynamics of 2 and 3 have been studied by ¹³C NMR spectroscopy, including variable-temperature and ¹³C-¹³C COSY experiments.

Original language	English
Pages (from-to)	4030-4036
Number of pages	7
Journal	Organometallics
Volume	17
Issue number	18
DOIs	https://doi.org/10.1021/om980486g
Publication status	Published - 1998 Aug 31
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Substitution of [Ru10C2(CO)24]2- with allene. Reversible formation of [Ru10C2(CO)22(μ-η2:η 2-C3H4)]2- and [Ru10C2(CO)20(μ-η2",

abstract = "Substitution of carbonyl ligands in [Ru10C2(CO)24]2- (1) by allene (1,2-propadiene) proceeds cleanly in diglyme at 90°C (1 atm) to afford the monoallene derivative [Ru10C2(CO)22(μ-η2: η2-C3H4)]2- (2). Treatment of either 1 or 2 with allene at 140°C (1 atm) forms the disubstituted derivative [Ru10C2(CO)20(μ-η2:η 2-C3H4)2]2- (3) in high yield. The new clusters have been isolated as salts with [PPN]+ or [PPh3CH2CH2PPh3]2+ counterions and have been characterized by analytical, spectroscopic, and X-ray crystallographic methods. The framework structures of both molecular cluster anions 2 and 3 are based on edge-shared bioctahedra, with the allene ligands bridging one or two pairs of apical positions, respectively. The idealized symmetries are C2 for 2 and D2 for 3. The solution structures and dynamics of 2 and 3 have been studied by 13C NMR spectroscopy, including variable-temperature and 13C-13C COSY experiments.",

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T1 - Substitution of [Ru10C2(CO)24]2- with allene. Reversible formation of [Ru10C2(CO)22(μ-η2:η 2-C3H4)]2- and [Ru10C2(CO)20(μ-η2

AU - Lee, Kwangyeol

AU - Shapley, John R.

PY - 1998/8/31

Y1 - 1998/8/31

N2 - Substitution of carbonyl ligands in [Ru10C2(CO)24]2- (1) by allene (1,2-propadiene) proceeds cleanly in diglyme at 90°C (1 atm) to afford the monoallene derivative [Ru10C2(CO)22(μ-η2: η2-C3H4)]2- (2). Treatment of either 1 or 2 with allene at 140°C (1 atm) forms the disubstituted derivative [Ru10C2(CO)20(μ-η2:η 2-C3H4)2]2- (3) in high yield. The new clusters have been isolated as salts with [PPN]+ or [PPh3CH2CH2PPh3]2+ counterions and have been characterized by analytical, spectroscopic, and X-ray crystallographic methods. The framework structures of both molecular cluster anions 2 and 3 are based on edge-shared bioctahedra, with the allene ligands bridging one or two pairs of apical positions, respectively. The idealized symmetries are C2 for 2 and D2 for 3. The solution structures and dynamics of 2 and 3 have been studied by 13C NMR spectroscopy, including variable-temperature and 13C-13C COSY experiments.

AB - Substitution of carbonyl ligands in [Ru10C2(CO)24]2- (1) by allene (1,2-propadiene) proceeds cleanly in diglyme at 90°C (1 atm) to afford the monoallene derivative [Ru10C2(CO)22(μ-η2: η2-C3H4)]2- (2). Treatment of either 1 or 2 with allene at 140°C (1 atm) forms the disubstituted derivative [Ru10C2(CO)20(μ-η2:η 2-C3H4)2]2- (3) in high yield. The new clusters have been isolated as salts with [PPN]+ or [PPh3CH2CH2PPh3]2+ counterions and have been characterized by analytical, spectroscopic, and X-ray crystallographic methods. The framework structures of both molecular cluster anions 2 and 3 are based on edge-shared bioctahedra, with the allene ligands bridging one or two pairs of apical positions, respectively. The idealized symmetries are C2 for 2 and D2 for 3. The solution structures and dynamics of 2 and 3 have been studied by 13C NMR spectroscopy, including variable-temperature and 13C-13C COSY experiments.

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Substitution of [Ru₁₀C₂(CO)₂₄]^2- with allene. Reversible formation of [Ru₁₀C₂(CO)₂₂(μ-η²:η ²-C₃H₄)]^2- and [Ru₁₀C₂(CO)₂₀(μ-η²

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