Journal
ORGANOMETALLICS
Volume 32, Issue 9, Pages 2795-2803Publisher
AMER CHEMICAL SOC
DOI: 10.1021/om400225j
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Funding
- Ministry of Education, Culture, Sports, Science and Technology of Japan [22350024, 23750053]
- Grants-in-Aid for Scientific Research [23750053, 25410058, 22350024] Funding Source: KAKEN
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The (eta(3)-alpha-silabenzyl)molybdenum complex Cp*Mo(CO)(2){eta(3)(Si,C,C)-Si(p-Tol)(3)} (1; Cp* = eta(5)-C5Me5, p-Tol = p-C6H4Me) was synthesized in high yield by removal of 4-(dimethylamino)pyridine (DMAP) from the (arylsilyl)(DMAP)molybdenum complex Cp*Mo(CO)(2)(DMAP){Si(p-Tol)(3)} (2) with BPh3. The precursor, complex 2, was readily prepared by reaction of the (DMAP)(methyl)molybdenum complex Cp*Mo(CO)(2)(DMAP)Me (3) with tri-p-tolylsilane (HSi(p-Tol)(3)) through methane elimination. Study on the reactivity of 1 toward DMAP and nitrile revealed that complex 1 serves as a synthetic equivalent of the 16-electron silyl complex Cp*Mo(CO)(2){Si(p-Tol)(3)}. Thus, complex 1 reacted with DMAP quantitatively at room temperature to reproduce arylsilyl complex 2 through dissociation of the arene carbon atoms coordinated to molybdenum. Complex 1 also reacted with acetonitrile at room temperature to give the N-silyliminoacyl complex Cp*Mo(CO)(2){eta(2)(C,N)-C(Me)=NSi(p-Tol)(3)} (4) exclusively via cleavage of the Mo-C(arene) bonds followed by insertion of nitrile into the Mo-Si bond.
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