TY - JOUR
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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U2 - 10.1016/j.ica.2003.11.014
DO - 10.1016/j.ica.2003.11.014
M3 - Article
AN - SCOPUS:1842476166
VL - 357
SP - 1854
EP - 1864
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
IS - 6
ER -