TY - JOUR
T1 - Photoreactions of silyliron(II) complexes Cp{black star}Fe(CO)2SiMe3 (CP{black star} η5-C5H5, η5-C5Me5) in the presence of trihydrosilanes
AU - Kawano, Yasuro
AU - Tobita, Hiromi
AU - Ogino, Hiroshi
N1 - Funding Information:
This work was supportedb y a Grant-in-Aid for Scientific Researcho n Priority Area of Organic Unusual Valency, No. 03233201fr, om the Ministry of Education, Sciencea nd Culture, and a Grant-in-Aid from the NissanS cienceF oundation.W e are gratefult o Shin-Etsu ChemicalC o., Ltd. for a gift of silicon compounds.
PY - 1992/4/28
Y1 - 1992/4/28
N2 - The photochemistry of silyliron(II) complexes Cp{black star}Fe(CO)2SiMe3 (Cp{black star} η5-C5H5, η5-C5Me5) in the presence of trihydrosilanes is described. Three types of products were observed, depending on the bulkiness of the Cp{black star} ligands and the substituents on the trihydrosilanes: (η5-C5H5)Fe(CO)2SiMe3 reacts with tert-alkylsilanes RSiH3 (R tBu, C(Me2)2H) upon irradiation to give silylene-bridged diiron complexes (η5-C5H5)2Fe2(CO)3(μ-SiHR) in good yields. In contrast, (η5-C5Me5)Fe(CO)2SiMe3 reacts with the tert-alkylsilanes photochemically to give silyl monoiron complexes (η5-C5Me5)Fe(CO)2SiH2R exclusively. Using p-TolSiH3 instead of tert-alkylsilane, the main photolysis product was the hydridobis(silyl)iron complex Cp{black star}Fe(CO)SiMe3(H)SiH2-p-Tol. The X-ray crystal structure analysis of (η5-C5H5)2Fe2(CO)3(μ-SiHtBu) revealed that this complex adopts a geometry in which the two Cp rings and a SiH bond are located on the same side with respect to the SiFe2C four-membered ring. 29Si NMR spectra of the silylene-bridged diiron complexes showed signals at remarkably low field (δ 235.5-289.1 ppm). A mechanism for the formation of these silylene-bridged diiron complexes is proposed.
AB - The photochemistry of silyliron(II) complexes Cp{black star}Fe(CO)2SiMe3 (Cp{black star} η5-C5H5, η5-C5Me5) in the presence of trihydrosilanes is described. Three types of products were observed, depending on the bulkiness of the Cp{black star} ligands and the substituents on the trihydrosilanes: (η5-C5H5)Fe(CO)2SiMe3 reacts with tert-alkylsilanes RSiH3 (R tBu, C(Me2)2H) upon irradiation to give silylene-bridged diiron complexes (η5-C5H5)2Fe2(CO)3(μ-SiHR) in good yields. In contrast, (η5-C5Me5)Fe(CO)2SiMe3 reacts with the tert-alkylsilanes photochemically to give silyl monoiron complexes (η5-C5Me5)Fe(CO)2SiH2R exclusively. Using p-TolSiH3 instead of tert-alkylsilane, the main photolysis product was the hydridobis(silyl)iron complex Cp{black star}Fe(CO)SiMe3(H)SiH2-p-Tol. The X-ray crystal structure analysis of (η5-C5H5)2Fe2(CO)3(μ-SiHtBu) revealed that this complex adopts a geometry in which the two Cp rings and a SiH bond are located on the same side with respect to the SiFe2C four-membered ring. 29Si NMR spectra of the silylene-bridged diiron complexes showed signals at remarkably low field (δ 235.5-289.1 ppm). A mechanism for the formation of these silylene-bridged diiron complexes is proposed.
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U2 - 10.1016/0022-328X(92)83224-6
DO - 10.1016/0022-328X(92)83224-6
M3 - Article
AN - SCOPUS:0001111312
VL - 428
SP - 125
EP - 143
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 1-2
ER -