Reactions of perfluoroalkyl-substituted phosphines with osmium carbonyl clusters: Crystal structures of bridged, linked and substituted derivatives

How Ghee Ang; Cheng Heng Koh; Lip Lin Koh; Whei Lu Kwik; Weng Kee Leong; Weng Yuen Leong

doi:10.1039/DT9930000847

Reactions of perfluoroalkyl-substituted phosphines with osmium carbonyl clusters: Crystal structures of bridged, linked and substituted derivatives

How Ghee Ang^*, Cheng Heng Koh, Lip Lin Koh, Whei Lu Kwik, Weng Kee Leong, Weng Yuen Leong

^*Corresponding author for this work

National University of Singapore

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

33 Citations (Scopus)

Abstract

The secondary phosphine (CF₃)₂C(OH)PH(CF₃) has been shown from ¹H and ¹⁹F NMR and single-crystal X-ray diffraction studies to undergo P-C bond cleavage upon reaction with [Os₃(CO)₁₁(MeCN)] to afford the phosphido-bridged cluster [Os₃(μ-H)(CO)₁₀{μ-PH(CF₃)}] 1 and the linked cluster [{Os₃(μ-H)(CO)₁₁}{μ-PH(CF₃)}{Os ₃(CO)₁₁}] 2. However, its reaction with [Os₃(CO)₁₀(MeCN)₂] afforded the novel molecule [Os₃(μ-H)(CO)₉{μ-HN=C(Me)P(CF₃)}] 3 the molecular structure of which has also been established. Compound 1 was also obtained from the reaction of (CF₃)₂C(OH)PH(CF₃) or PH(CF₃)₂ with the anionic cluster [Os₃H(CO)₁₁]^-. Furthermore the primary phosphines (CF₃)₂C(OH)PH₂ and PH₂(CF₃) display similar P-C bond cleavage upon reactions with [Os₃H(CO)₁₁]^- to afford the phosphido-bridged cluster [Os₃(μ-H)(CO)₁₀(μ-PH₂)]. On the other hand, (CF₃)₂C(OH)PH₂ gave simple substitution products upon reactions with [Os₃(CO)₁₀(MeCN)₂] and [Os₃(CO)₁₁(MeCN)], as has been found for the tertiary phosphine P(CF₃)₃. Compound 2 represents the first example of two triosmium triangles linked by a terminally co-ordinated PR₂ group.

Original language	English
Pages (from-to)	847-855
Number of pages	9
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	6
DOIs	https://doi.org/10.1039/DT9930000847
Publication status	Published - 1993
Externally published	Yes

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General Chemistry

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@article{9474ba8139914b68bdcb4130ffd266b7,

title = "Reactions of perfluoroalkyl-substituted phosphines with osmium carbonyl clusters: Crystal structures of bridged, linked and substituted derivatives",

abstract = "The secondary phosphine (CF3)2C(OH)PH(CF3) has been shown from 1H and 19F NMR and single-crystal X-ray diffraction studies to undergo P-C bond cleavage upon reaction with [Os3(CO)11(MeCN)] to afford the phosphido-bridged cluster [Os3(μ-H)(CO)10\{μ-PH(CF3)\}] 1 and the linked cluster [\{Os3(μ-H)(CO)11\}\{μ-PH(CF3)\}\{Os 3(CO)11\}] 2. However, its reaction with [Os3(CO)10(MeCN)2] afforded the novel molecule [Os3(μ-H)(CO)9\{μ-HN=C(Me)P(CF3)\}] 3 the molecular structure of which has also been established. Compound 1 was also obtained from the reaction of (CF3)2C(OH)PH(CF3) or PH(CF3)2 with the anionic cluster [Os3H(CO)11]-. Furthermore the primary phosphines (CF3)2C(OH)PH2 and PH2(CF3) display similar P-C bond cleavage upon reactions with [Os3H(CO)11]- to afford the phosphido-bridged cluster [Os3(μ-H)(CO)10(μ-PH2)]. On the other hand, (CF3)2C(OH)PH2 gave simple substitution products upon reactions with [Os3(CO)10(MeCN)2] and [Os3(CO)11(MeCN)], as has been found for the tertiary phosphine P(CF3)3. Compound 2 represents the first example of two triosmium triangles linked by a terminally co-ordinated PR2 group.",

author = "Ang, \{How Ghee\} and Koh, \{Cheng Heng\} and Koh, \{Lip Lin\} and Kwik, \{Whei Lu\} and Leong, \{Weng Kee\} and Leong, \{Weng Yuen\}",

year = "1993",

doi = "10.1039/DT9930000847",

language = "English",

pages = "847--855",

journal = "Journal of the Chemical Society. Dalton Transactions",

issn = "1472-7773",

publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Reactions of perfluoroalkyl-substituted phosphines with osmium carbonyl clusters

T2 - Crystal structures of bridged, linked and substituted derivatives

AU - Ang, How Ghee

AU - Koh, Cheng Heng

AU - Koh, Lip Lin

AU - Kwik, Whei Lu

AU - Leong, Weng Kee

AU - Leong, Weng Yuen

PY - 1993

Y1 - 1993

N2 - The secondary phosphine (CF3)2C(OH)PH(CF3) has been shown from 1H and 19F NMR and single-crystal X-ray diffraction studies to undergo P-C bond cleavage upon reaction with [Os3(CO)11(MeCN)] to afford the phosphido-bridged cluster [Os3(μ-H)(CO)10{μ-PH(CF3)}] 1 and the linked cluster [{Os3(μ-H)(CO)11}{μ-PH(CF3)}{Os 3(CO)11}] 2. However, its reaction with [Os3(CO)10(MeCN)2] afforded the novel molecule [Os3(μ-H)(CO)9{μ-HN=C(Me)P(CF3)}] 3 the molecular structure of which has also been established. Compound 1 was also obtained from the reaction of (CF3)2C(OH)PH(CF3) or PH(CF3)2 with the anionic cluster [Os3H(CO)11]-. Furthermore the primary phosphines (CF3)2C(OH)PH2 and PH2(CF3) display similar P-C bond cleavage upon reactions with [Os3H(CO)11]- to afford the phosphido-bridged cluster [Os3(μ-H)(CO)10(μ-PH2)]. On the other hand, (CF3)2C(OH)PH2 gave simple substitution products upon reactions with [Os3(CO)10(MeCN)2] and [Os3(CO)11(MeCN)], as has been found for the tertiary phosphine P(CF3)3. Compound 2 represents the first example of two triosmium triangles linked by a terminally co-ordinated PR2 group.

AB - The secondary phosphine (CF3)2C(OH)PH(CF3) has been shown from 1H and 19F NMR and single-crystal X-ray diffraction studies to undergo P-C bond cleavage upon reaction with [Os3(CO)11(MeCN)] to afford the phosphido-bridged cluster [Os3(μ-H)(CO)10{μ-PH(CF3)}] 1 and the linked cluster [{Os3(μ-H)(CO)11}{μ-PH(CF3)}{Os 3(CO)11}] 2. However, its reaction with [Os3(CO)10(MeCN)2] afforded the novel molecule [Os3(μ-H)(CO)9{μ-HN=C(Me)P(CF3)}] 3 the molecular structure of which has also been established. Compound 1 was also obtained from the reaction of (CF3)2C(OH)PH(CF3) or PH(CF3)2 with the anionic cluster [Os3H(CO)11]-. Furthermore the primary phosphines (CF3)2C(OH)PH2 and PH2(CF3) display similar P-C bond cleavage upon reactions with [Os3H(CO)11]- to afford the phosphido-bridged cluster [Os3(μ-H)(CO)10(μ-PH2)]. On the other hand, (CF3)2C(OH)PH2 gave simple substitution products upon reactions with [Os3(CO)10(MeCN)2] and [Os3(CO)11(MeCN)], as has been found for the tertiary phosphine P(CF3)3. Compound 2 represents the first example of two triosmium triangles linked by a terminally co-ordinated PR2 group.

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Reactions of perfluoroalkyl-substituted phosphines with osmium carbonyl clusters: Crystal structures of bridged, linked and substituted derivatives

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