Formation and reactivity of a transient cationic alkyl phosphinidene complex

Rakesh A. Rajagopalan; Brian T. Sterenberg

doi:10.1021/om101025c

Formation and reactivity of a transient cationic alkyl phosphinidene complex

Rakesh A. Rajagopalan, Brian T. Sterenberg

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

20 Citations (Scopus)

Abstract

Reaction of the chloroisopropylphosphido complex [Cp*Mo(CO) ₃{P(Cl)i-Pr}] (1) with AlCl₃ generates the transient cationic alkylphosphinidene complex [Cp*Mo(CO)₃ {P(i-Pr)}][AlCl₄] (2). If it is generated in the presence of diphenylacetylene, 2 undergoes a (1 + 2) cycloaddition to form the phosphirene complex [Cp*Mo(CO)₃{P(i-Pr)C(Ph)C- (Ph)}][AlCl₄] (3). Reaction of 2 with PPh₃ forms the phosphine- coordinated phosphinidene complex [Cp*Mo(CO)₃{P(PPh₃)(i-Pr)}] [AlCl₄] (4). Compound 2 reacts with Ph₂SiH₂ to insert the phosphinidene phosphorus atom into the Si-H bond, forming the secondary silylphosphine complex [Cp*Mo(CO)₃ {P(H)(SiHPh ₂)(i-Pr)}][AlCl₄] (5). Similarly, 2 reacts with ferrocene to activate a C-H bond, resulting in the formation of [Cp*Mo(CO) ₃{P(H)(i-Pr)(C₅H₄FeC₅H ₅)}][AlCl₄] (6).

Original language	English
Pages (from-to)	2933-2938
Number of pages	6
Journal	Organometallics
Volume	30
Issue number	11
DOIs	https://doi.org/10.1021/om101025c
Publication status	Published - May 17 2011
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Formation and reactivity of a transient cationic alkyl phosphinidene complex",

abstract = "Reaction of the chloroisopropylphosphido complex [Cp*Mo(CO) 3{P(Cl)i-Pr}] (1) with AlCl3 generates the transient cationic alkylphosphinidene complex [Cp*Mo(CO)3 {P(i-Pr)}][AlCl4] (2). If it is generated in the presence of diphenylacetylene, 2 undergoes a (1 + 2) cycloaddition to form the phosphirene complex [Cp*Mo(CO)3{P(i-Pr)C(Ph)C- (Ph)}][AlCl4] (3). Reaction of 2 with PPh3 forms the phosphine- coordinated phosphinidene complex [Cp*Mo(CO)3{P(PPh3)(i-Pr)}] [AlCl4] (4). Compound 2 reacts with Ph2SiH2 to insert the phosphinidene phosphorus atom into the Si-H bond, forming the secondary silylphosphine complex [Cp*Mo(CO)3 {P(H)(SiHPh 2)(i-Pr)}][AlCl4] (5). Similarly, 2 reacts with ferrocene to activate a C-H bond, resulting in the formation of [Cp*Mo(CO) 3{P(H)(i-Pr)(C5H4FeC5H 5)}][AlCl4] (6).",

author = "Rajagopalan, {Rakesh A.} and Sterenberg, {Brian T.}",

year = "2011",

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doi = "10.1021/om101025c",

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AU - Sterenberg, Brian T.

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N2 - Reaction of the chloroisopropylphosphido complex [Cp*Mo(CO) 3{P(Cl)i-Pr}] (1) with AlCl3 generates the transient cationic alkylphosphinidene complex [Cp*Mo(CO)3 {P(i-Pr)}][AlCl4] (2). If it is generated in the presence of diphenylacetylene, 2 undergoes a (1 + 2) cycloaddition to form the phosphirene complex [Cp*Mo(CO)3{P(i-Pr)C(Ph)C- (Ph)}][AlCl4] (3). Reaction of 2 with PPh3 forms the phosphine- coordinated phosphinidene complex [Cp*Mo(CO)3{P(PPh3)(i-Pr)}] [AlCl4] (4). Compound 2 reacts with Ph2SiH2 to insert the phosphinidene phosphorus atom into the Si-H bond, forming the secondary silylphosphine complex [Cp*Mo(CO)3 {P(H)(SiHPh 2)(i-Pr)}][AlCl4] (5). Similarly, 2 reacts with ferrocene to activate a C-H bond, resulting in the formation of [Cp*Mo(CO) 3{P(H)(i-Pr)(C5H4FeC5H 5)}][AlCl4] (6).

AB - Reaction of the chloroisopropylphosphido complex [Cp*Mo(CO) 3{P(Cl)i-Pr}] (1) with AlCl3 generates the transient cationic alkylphosphinidene complex [Cp*Mo(CO)3 {P(i-Pr)}][AlCl4] (2). If it is generated in the presence of diphenylacetylene, 2 undergoes a (1 + 2) cycloaddition to form the phosphirene complex [Cp*Mo(CO)3{P(i-Pr)C(Ph)C- (Ph)}][AlCl4] (3). Reaction of 2 with PPh3 forms the phosphine- coordinated phosphinidene complex [Cp*Mo(CO)3{P(PPh3)(i-Pr)}] [AlCl4] (4). Compound 2 reacts with Ph2SiH2 to insert the phosphinidene phosphorus atom into the Si-H bond, forming the secondary silylphosphine complex [Cp*Mo(CO)3 {P(H)(SiHPh 2)(i-Pr)}][AlCl4] (5). Similarly, 2 reacts with ferrocene to activate a C-H bond, resulting in the formation of [Cp*Mo(CO) 3{P(H)(i-Pr)(C5H4FeC5H 5)}][AlCl4] (6).

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Formation and reactivity of a transient cationic alkyl phosphinidene complex

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