sp3 C-H and sp2 C-H agostic ruthenium complexes: A combined experimental and theoretical study

Milko E. Van Der Boom; Mark A. Iron; Onur Atasoylu; Linda J.W. Shimon; Haim Rozenberg; Yehoshoa Ben-David; Leonid Konstantinovski; Jan M.L. Martin; David Milstein

doi:10.1016/j.ica.2003.11.014

sp³ C-H and sp² C-H agostic ruthenium complexes: A combined experimental and theoretical study

Milko E. Van Der Boom, Mark A. Iron, Onur Atasoylu, Linda J.W. Shimon, Haim Rozenberg, Yehoshoa Ben-David, Leonid Konstantinovski, Jan M.L. Martin, David Milstein

Weizmann Institute of Science, Israel

Research output: Contribution to journal › Article

46 Citations (Scopus)

Abstract

Halide abstraction from the 18 electron Ru(II) complex RuCl(CO) ₂[2,6-(CH₂P^tBu₂)₂C ₆H₃] (2) with AgPF₆ results in the exclusive formation of the cationic complex {Ru(CO)₂[2,6-(CH₂P ^tBu₂)₂C₆H₃]} ⁺PF₆^- (3). The molecular structures of 2 and 3 were determined by complete single-crystal diffraction studies. X-ray crystallographic analysis of 3 reveals that the "open" coordination site is occupied by an agostic interaction between the metal center and an sp³ C-H bond of a tert-butyl substituent. DFT gas phase calculations (B97-1/SDD) show the necessity of two sterically demanding tert-butyl substituents on one P donor atom for the agostic interaction to occur. The reaction of 3 with H₂ results in the quantitative conversion to {Ru(H)(CO)₂[2,6-(CH₂P^tBu₂) ₂C₆H₄]}⁺PF₆^- (4) where the aromatic C_ipso-H bond is η²-coordinated to the metal center. Treatment of the agostic complex 4 with Et₃N results in the formation of the neutral complex Ru(H)(CO)₂[2,6- (CH₂P^tBu₂)₂C₆H ₃] (5). The mechanistic details of 3+H₂→4 were investigated by DFT calculations at the B97-1/SDB-cc-pVDZ//B97-1/SDD level of theory.

Original language	English
Pages (from-to)	1854-1864
Number of pages	11
Journal	Inorganica Chimica Acta
Volume	357
Issue number	6
DOIs	https://doi.org/10.1016/j.ica.2003.11.014
Publication status	Published - Apr 20 2004

Keywords

Agostic interactions
Crystal structures
DFT
Dihydrogen addition
Pincer complexes
Ruthenium

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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Van Der Boom, M. E., Iron, M. A., Atasoylu, O., Shimon, L. J. W., Rozenberg, H., Ben-David, Y., Konstantinovski, L., Martin, J. M. L., & Milstein, D. (2004). sp³ C-H and sp² C-H agostic ruthenium complexes: A combined experimental and theoretical study. Inorganica Chimica Acta, 357(6), 1854-1864. https://doi.org/10.1016/j.ica.2003.11.014

sp³ C-H and sp² C-H agostic ruthenium complexes : A combined experimental and theoretical study. / Van Der Boom, Milko E.; Iron, Mark A.; Atasoylu, Onur; Shimon, Linda J.W.; Rozenberg, Haim; Ben-David, Yehoshoa; Konstantinovski, Leonid; Martin, Jan M.L.; Milstein, David.

In: Inorganica Chimica Acta, Vol. 357, No. 6, 20.04.2004, p. 1854-1864.

Research output: Contribution to journal › Article

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title = "sp3 C-H and sp2 C-H agostic ruthenium complexes: A combined experimental and theoretical study",

abstract = "Halide abstraction from the 18 electron Ru(II) complex RuCl(CO) 2[2,6-(CH2PtBu2)2C 6H3] (2) with AgPF6 results in the exclusive formation of the cationic complex {Ru(CO)2[2,6-(CH2P tBu2)2C6H3]} +PF6- (3). The molecular structures of 2 and 3 were determined by complete single-crystal diffraction studies. X-ray crystallographic analysis of 3 reveals that the {"}open{"} coordination site is occupied by an agostic interaction between the metal center and an sp3 C-H bond of a tert-butyl substituent. DFT gas phase calculations (B97-1/SDD) show the necessity of two sterically demanding tert-butyl substituents on one P donor atom for the agostic interaction to occur. The reaction of 3 with H2 results in the quantitative conversion to {Ru(H)(CO)2[2,6-(CH2PtBu2) 2C6H4]}+PF6- (4) where the aromatic Cipso-H bond is η2-coordinated to the metal center. Treatment of the agostic complex 4 with Et3N results in the formation of the neutral complex Ru(H)(CO)2[2,6- (CH2PtBu2)2C6H 3] (5). The mechanistic details of 3+H2→4 were investigated by DFT calculations at the B97-1/SDB-cc-pVDZ//B97-1/SDD level of theory.",

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T1 - sp3 C-H and sp2 C-H agostic ruthenium complexes

T2 - A combined experimental and theoretical study

AU - Van Der Boom, Milko E.

AU - Iron, Mark A.

AU - Atasoylu, Onur

AU - Shimon, Linda J.W.

AU - Rozenberg, Haim

AU - Ben-David, Yehoshoa

AU - Konstantinovski, Leonid

AU - Martin, Jan M.L.

AU - Milstein, David

PY - 2004/4/20

Y1 - 2004/4/20

N2 - Halide abstraction from the 18 electron Ru(II) complex RuCl(CO) 2[2,6-(CH2PtBu2)2C 6H3] (2) with AgPF6 results in the exclusive formation of the cationic complex {Ru(CO)2[2,6-(CH2P tBu2)2C6H3]} +PF6- (3). The molecular structures of 2 and 3 were determined by complete single-crystal diffraction studies. X-ray crystallographic analysis of 3 reveals that the "open" coordination site is occupied by an agostic interaction between the metal center and an sp3 C-H bond of a tert-butyl substituent. DFT gas phase calculations (B97-1/SDD) show the necessity of two sterically demanding tert-butyl substituents on one P donor atom for the agostic interaction to occur. The reaction of 3 with H2 results in the quantitative conversion to {Ru(H)(CO)2[2,6-(CH2PtBu2) 2C6H4]}+PF6- (4) where the aromatic Cipso-H bond is η2-coordinated to the metal center. Treatment of the agostic complex 4 with Et3N results in the formation of the neutral complex Ru(H)(CO)2[2,6- (CH2PtBu2)2C6H 3] (5). The mechanistic details of 3+H2→4 were investigated by DFT calculations at the B97-1/SDB-cc-pVDZ//B97-1/SDD level of theory.

AB - Halide abstraction from the 18 electron Ru(II) complex RuCl(CO) 2[2,6-(CH2PtBu2)2C 6H3] (2) with AgPF6 results in the exclusive formation of the cationic complex {Ru(CO)2[2,6-(CH2P tBu2)2C6H3]} +PF6- (3). The molecular structures of 2 and 3 were determined by complete single-crystal diffraction studies. X-ray crystallographic analysis of 3 reveals that the "open" coordination site is occupied by an agostic interaction between the metal center and an sp3 C-H bond of a tert-butyl substituent. DFT gas phase calculations (B97-1/SDD) show the necessity of two sterically demanding tert-butyl substituents on one P donor atom for the agostic interaction to occur. The reaction of 3 with H2 results in the quantitative conversion to {Ru(H)(CO)2[2,6-(CH2PtBu2) 2C6H4]}+PF6- (4) where the aromatic Cipso-H bond is η2-coordinated to the metal center. Treatment of the agostic complex 4 with Et3N results in the formation of the neutral complex Ru(H)(CO)2[2,6- (CH2PtBu2)2C6H 3] (5). The mechanistic details of 3+H2→4 were investigated by DFT calculations at the B97-1/SDB-cc-pVDZ//B97-1/SDD level of theory.

KW - Agostic interactions

KW - Crystal structures

KW - DFT

KW - Dihydrogen addition

KW - Pincer complexes

KW - Ruthenium

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JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

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