[(carbonyl)2(tris(3,5-dimethylpyrazolyl)borate)tungsten(C(OH)N(n-Bu)C(Me)NH)]BF4*CH2Cl2 | 154991-34-1

• 英文名称: [(carbonyl)2(tris(3,5-dimethylpyrazolyl)borate)tungsten(C(OH)N(n-Bu)C(Me)NH)]BF4*CH2Cl2
• CAS: 154991-34-1
• 化学式: BF₄*CH₂Cl₂*C₂₄H₃₆BN₈O₃W
• 分子量: 851.0
• InChiKey: PMBGVUUUQXTWNJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  [(carbonyl)2(tris(3,5-dimethylpyrazolyl)borate)tungsten(II)(C(O)N(n-Bu)C(Me)NH)]*0.5CH2Cl2 、 tetrafluoroboric acid dimethyl ether complex 以 二氯甲烷 为溶剂， 以73%的产率得到[(carbonyl)2(tris(3,5-dimethylpyrazolyl)borate)tungsten(C(OH)N(n-Bu)C(Me)NH)]BF4*CH2Cl2
  参考文献：
  名称：

  钨（II）配合物中胺诱导的羰基和腈配体的偶联

  摘要：

  Reaction of [Tp'(CO)3W(N=CMe)][BF4] (1), an intermediate formed in situ from Tp'W-(CO)3I and AgBF4 in acetonitrile, with ammonia or n-butylamine generates neutral complexes of the type Tp'(CO)2W-C(=O)-N(R)-C(Me)=N(H) (R = H (2), n-butyl (3)). Protonation of these heteroatom metallacycle complexes occurs at the acyl oxygen atom to produce cationic metallacycle hydroxycarbene complexes, [Tp'(CO)2W=C(OH)-N(R)-C(Me)=N(H)][BF4] (R = H (4), n-butyl (5)). NMR spectra and a single crystal X-ray structure indicate that the five-membered ring is planar and effectively lies in the molecular mirror plane with the carbene carbon adjacent to the two terminal carbonyl ligands. Methylation of the metallacycle acyl complexes at the acyl oxygen produces analogous cationic metallacycle methoxycarbene complexes of the type [Tp'(CO)2W=C(OMe)-N(R)-C(Me)=N(H)][CF3SO3] (R = H (6), n-butyl (7)). Reaction of the [Tp'(CO)3W(N=CMe)][BF4] intermediate with the bulky tert-butylamine nucleophile results in formation of an unusual amido complex, Tp'(CO)2W-N-C(=CH2)-N(Bu(t))C(=O) (8), with the original nitrile nitrogen now three-coordinate and bound to the metal and both carbons of the four-membered ring. Donation of the lone pair of electrons on the nitrogen of the amido ligand to the tungsten center is reflected by the low IR stretching frequencies of the carbonyl ligands and their downfield carbon resonance in the C-13 NMR. NMR spectra and an X-ray structure indicate that the planar four-membered, ring of the amido ligand lies on the molecular mirror plane.

  DOI：

  10.1021/om00016a026