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

45 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

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Keywords

Agostic interactions
Crystal structures
DFT
Dihydrogen addition
Pincer complexes
Ruthenium

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Cite this

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.

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KW - DFT

KW - Dihydrogen addition

KW - Pincer complexes

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JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

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10.1016/j.ica.2003.11.014