Arene C-H Bond Coordination versus C-H Bond Cleavage in Low-Valent Group 6 Carbonyl Pincer Complexes

Sara R.M.M. De Aguiar; Berthold Stöger; Ernst Pittenauer; Günter Allmaier; Luis F. Veiros; Karl Kirchner

doi:10.1021/acs.organomet.6b00563

Arene C-H Bond Coordination versus C-H Bond Cleavage in Low-Valent Group 6 Carbonyl Pincer Complexes

Sara R.M.M. De Aguiar, Berthold Stöger, Ernst Pittenauer, Günter Allmaier, Luis F. Veiros, Karl Kirchner

Department of Chemistry

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

14 Citations (SciVal)

Abstract

The reaction of hexacarbonyl group 6 complexes with the P(CH)P ligand N,N′-bis(diisopropylphosphino)-N,N′-dimethyl-1,3-diaminobenzene was investigated. The objective was to obtain PCP pincer complexes via directed C-H bond activation and cleavage. In the case of chromium and molybdenum, complexes [Cr(κ³P,CH,P-P(CH)P^NMe-iPr)(CO)₃] and [Mo(κ³P,CH,P-P(CH)P^NMe-iPr)(CO)₃], featuring η²-C_aryl-H bonds, were formed and no C-H bond cleavage took place. With tungsten the expected seven-coordinate hydrido carbonyl W(II) complex [W(κ³P,C,P-PCP^NMe-iPr)(CO)₃H] was formed. DFT mechanistic studies corroborate the experimental observations and indicate that the M-H bond strength grows in the order Cr-H < Mo-H < W-H, explaining the preference for the hydride complex only in the case of W. X-ray structures of these complexes are presented.

Original language	English
Pages (from-to)	3032-3039
Number of pages	8
Journal	Organometallics
Volume	35
Issue number	17
DOIs	https://doi.org/10.1021/acs.organomet.6b00563
Publication status	Published - 12 Sept 2016

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Arene C-H Bond Coordination versus C-H Bond Cleavage in Low-Valent Group 6 Carbonyl Pincer Complexes",

abstract = "The reaction of hexacarbonyl group 6 complexes with the P(CH)P ligand N,N′-bis(diisopropylphosphino)-N,N′-dimethyl-1,3-diaminobenzene was investigated. The objective was to obtain PCP pincer complexes via directed C-H bond activation and cleavage. In the case of chromium and molybdenum, complexes [Cr(κ3P,CH,P-P(CH)PNMe-iPr)(CO)3] and [Mo(κ3P,CH,P-P(CH)PNMe-iPr)(CO)3], featuring η2-Caryl-H bonds, were formed and no C-H bond cleavage took place. With tungsten the expected seven-coordinate hydrido carbonyl W(II) complex [W(κ3P,C,P-PCPNMe-iPr)(CO)3H] was formed. DFT mechanistic studies corroborate the experimental observations and indicate that the M-H bond strength grows in the order Cr-H < Mo-H < W-H, explaining the preference for the hydride complex only in the case of W. X-ray structures of these complexes are presented.",

author = "{De Aguiar}, {Sara R.M.M.} and Berthold St{\"o}ger and Ernst Pittenauer and G{\"u}nter Allmaier and Veiros, {Luis F.} and Karl Kirchner",

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AU - De Aguiar, Sara R.M.M.

AU - Stöger, Berthold

AU - Pittenauer, Ernst

AU - Allmaier, Günter

AU - Veiros, Luis F.

AU - Kirchner, Karl

PY - 2016/9/12

Y1 - 2016/9/12

N2 - The reaction of hexacarbonyl group 6 complexes with the P(CH)P ligand N,N′-bis(diisopropylphosphino)-N,N′-dimethyl-1,3-diaminobenzene was investigated. The objective was to obtain PCP pincer complexes via directed C-H bond activation and cleavage. In the case of chromium and molybdenum, complexes [Cr(κ3P,CH,P-P(CH)PNMe-iPr)(CO)3] and [Mo(κ3P,CH,P-P(CH)PNMe-iPr)(CO)3], featuring η2-Caryl-H bonds, were formed and no C-H bond cleavage took place. With tungsten the expected seven-coordinate hydrido carbonyl W(II) complex [W(κ3P,C,P-PCPNMe-iPr)(CO)3H] was formed. DFT mechanistic studies corroborate the experimental observations and indicate that the M-H bond strength grows in the order Cr-H < Mo-H < W-H, explaining the preference for the hydride complex only in the case of W. X-ray structures of these complexes are presented.

AB - The reaction of hexacarbonyl group 6 complexes with the P(CH)P ligand N,N′-bis(diisopropylphosphino)-N,N′-dimethyl-1,3-diaminobenzene was investigated. The objective was to obtain PCP pincer complexes via directed C-H bond activation and cleavage. In the case of chromium and molybdenum, complexes [Cr(κ3P,CH,P-P(CH)PNMe-iPr)(CO)3] and [Mo(κ3P,CH,P-P(CH)PNMe-iPr)(CO)3], featuring η2-Caryl-H bonds, were formed and no C-H bond cleavage took place. With tungsten the expected seven-coordinate hydrido carbonyl W(II) complex [W(κ3P,C,P-PCPNMe-iPr)(CO)3H] was formed. DFT mechanistic studies corroborate the experimental observations and indicate that the M-H bond strength grows in the order Cr-H < Mo-H < W-H, explaining the preference for the hydride complex only in the case of W. X-ray structures of these complexes are presented.

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ER -

Arene C-H Bond Coordination versus C-H Bond Cleavage in Low-Valent Group 6 Carbonyl Pincer Complexes

Abstract

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