Reaction of Zirconocene—Alkyne Complexes with Mo(CO)<sub>6</sub>.

Mito, Shizue; Zhou, Lishan; Xi, Chanjuan; Takahashi, Tamotsu

doi:10.1002/chin.200623055

Cited by 1 publication

(9 citation statements)

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“…There have been few other isolable monoiminoacyl group 4 complexes with the outside geometry. 37−43 However, at 80 °C in C 7 D 8 , 2 converts entirely to the inside isomer, as indicated by 1 H NMR (Figure S4).…”

Section: ■ Results and Discussionmentioning

confidence: 94%

“…The purity of 1 (>99%) was established by 1 H NMR. 1 (5.0 mg, 0.0128 mmol), predetermined amounts of excess CpCr-(CO) 3 H, (Me 2 SiO) 3 (1.0 mg) as internal standard, and 0.7 mL of C 6 D 6 as solvent. The reaction progress was monitored by 1 H NMR.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Kinetic study was carried out under pseudo-first-order condition (CpCr(CO) 3 H in excess); therefore, establishment of purity of 3 is not practical due to the remainingCpCr(CO) 3 H. Nonetheless, the conversion calculated from the limiting Cp* 2 Zr(CH 3 ) 2 is greater than 95%. 1 H NMR of 3 (126 MHz, C 6 D 6 , 298 K) δ 4.75 (s, Cp, 5H), 1.73 (s, C 5 Me 5, 30H), 0.13 (s, Me, 3H).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Crystals of compound 4 were obtained through diffusion of pentane into a toluene solution at −30 °C. The purity of 4 (>99%) was established by 1 5). To a 50 mL Schlenk flask were loaded 2 (23 mg, 0.048 mol), B(C 6 F 5 ) 3 (25 mg, 0.049 mmol), and 5 mL of dichloromethane.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…SC-XRD quality crystals was obtained through diffusion of pentane into a dichloromethane solution of 5 at −30 °C. The purity of 4 (>99%) was established by 1 [Cp* 2 Zr(η 2 -C,N-C{N t Bu}CH 3 )(CN t Bu)] + [H 3 CB(C 6 F 5 ) 3 ] − (5-CN t Bu). A J.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Insertion of Isonitriles into the Zr–CH₃ Bond of Cp*₂Zr(CH₃)₂ and Electrophilic Cleavage of the Remaining Methyl Group

Chen

Norton

et al. 2018

Organometallics

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The insertion of tert-butyl isonitrile ( t BuNC) into the M−C bond of Cp* 2 Zr(CH 3 ) 2 (1) leads to the formation of a monoiminoacyl product Cp* 2 Zr(iminoacyl)CH 3 (2). SC-XRD analysis has revealed that the η 2 coordinated iminoacyl ligand has an "N-outside" orientation. Compound 2 undergoes rapid Zr−C bond cleavage with the Brønsted acid CpCr(CO) 3 H or the Lewis acid B(C 6 F 5 ) 3 , yielding Zr cation 4 or 5 with the corresponding anion [MeB(C 6 F 5 ) 3 ] − or [CpCo(CO) 3 ] − . In the solid-state structure of 4, the Zr cation features an η 2 "N-inside" geometry for the iminoacyl group and interacts with the [CpCo(CO) 3 ] − via the oxygen atom of one of the CO ligands. Cleavage of the methyl ligand from the Zr of 1 with CpCr(CO) 3 H proceeds with a second-order rate constant k 1 of 2.11(4) × 10 −3 M −1 s −1 , whereas cleavage of the methyl ligand from the Zr of 2 is significantly faster, with an estimated k 2 greater than 10 4 M −1 s −1 . In light of the observed "N-outside" to "N-inside" change from 2 to 4, we propose that the enhanced rate with 2 is due to initial protonation of its nitrogen, subsequent outside-toinside rotation, and eventual transfer of the proton onto the Zr−C bond.

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Section: ■ Results and Discussionmentioning

confidence: 94%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

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