[(acetonitrile)tricarbonyl(tris(3,5-dimethylpyrazolyl)borate)tungsten(II)]BF4 | 154975-12-9

• 英文名称: [(acetonitrile)tricarbonyl(tris(3,5-dimethylpyrazolyl)borate)tungsten(II)]BF4
• CAS: 154975-12-9
• 化学式: BF₄*C₂₀H₂₅BN₇O₃W
• 分子量: 692.929
• InChiKey: XNPSBWSGOXDRHN-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  [(acetonitrile)tricarbonyl(tris(3,5-dimethylpyrazolyl)borate)tungsten(II)]BF4 在 LiBH₄ 作用下， 以 乙腈 为溶剂， 以55%的产率得到
  参考文献：
  名称：

  在低价羰基钨配合物中通过氮杂亚乙烯基将腈转化为腈

  摘要：

  Tp[prime](CO)[sub 2]W=N=CRNu 型氮杂亚乙烯基配合物可从 [Tp[prime](CO)[sub 3]W(N=CR)][BF[sub 4]] 与亲核试剂（Tp[prime] = 氢化三（3,5-二甲基吡唑基）硼酸盐；R = Me，Nu = H (1a)；R = Ph，Nu = Et (1d)；R = Me，Nu = MeO (1e))。相关的氮杂亚乙烯基配合物 Tp[prime](CO)[sub 2]W=N=CHR (R = Me (1a); R = Et (1b); R = CH[sub 2]Ph (1c)) 通过插入当金属试剂在腈存在下光解时，腈进入 Tp[prime](CO)[sub 3]WH 的 WH 键。从氮杂亚乙烯基氮到钨中心的孤对电子的捐赠，与电子计数指南兼容，反映在羰基配体的低红外伸缩频率及其在 [sup 15] C NMR 中的低场碳共振。Tp[prime](CO)[sub

  DOI：

  10.1021/ja00098a022
• 作为产物：
  描述：

  silver tetrafluoroborate 、 [WI(CO)₃(hydrotris(dimethylpyrazolyl)borate)] 以 乙腈 为溶剂， 生成 [(acetonitrile)tricarbonyl(tris(3,5-dimethylpyrazolyl)borate)tungsten(II)]BF4
  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