W2(neopentoxide)6 | 110116-70-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: W2(neopentoxide)6
• 英文别名: W2(OCH2-t-Bu)6
• CAS: 110116-70-6
• 化学式: C₃₀H₆₆O₆W₂
• 分子量: 890.55
• InChiKey: JNLXFDIYFRORLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.08
• 重原子数：
  38.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.38
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  W2(neopentoxide)6 在 ethylene 作用下， 以 not given 为溶剂， 生成 bis(η2-ethylene)hexakis(neopentoxy)ditungsten
  参考文献：
  名称：

  金属醇盐。金属氧化物模型。18. 双（η2-乙烯）六（新戊氧基）二钨的结构、键合和动态行为。钨-钨三键可逆加成碳-碳双键的研究

  摘要：

  W 2 (OCH 2 -t-Bu) 和乙烯 (≥2 当量) 的烃溶液在 0 o C 反应生成 W 2 (OCH 2 -t-Bu) 6 (η 2 -C 2 H 4 ) 2 ， 1，已通过核磁共振研究和单晶 X 射线衍射研究表征。1 在 -155 o C 的晶体数据：a=11.754 (4) A，b=31.405 (14) A，c=11.274 (4) A，β=104.96 (2) o 和空间群 P2 1 /c。

  DOI：

  10.1021/ja00048a022
• 作为产物：
  描述：

  新戊醇 、 以 甲苯 为溶剂， 生成 W2(neopentoxide)6
  参考文献：
  名称：

  Ring-Opening of σ-Thienyl and σ-Furyl Ligands at Ditungsten (M⋮M) Centers

  摘要：

  A series of compounds of formula 1,2-M(2)(sigma-Th)(2)(NMe(2))(4), 1, has been prepared, where M = Mo and/or W and Th = 2-thienyl[2-Th], 3-thienyl[3-Th], 5-methyl-2-thienyl[2,5-MeTh], and 2-benzothienyl[2-BTh]. In hydrocarbon solvents-these compounds exist as a mixture of anti and gauche rotamers having a central CN(2)M=MN(2)C core. Addition of (t)BuOH or CF(3)Me(2)COH to hydrocarbon solutions of 1, where M = W, lead to ring-opened products, 2, when the thienyl ligand is attached via the 2-carbon position. No ring-opening occurs for 3-thienyl derivatives. W-2(OR)(5) (mu-CCH2CHCHS) (sigma-2-Th), 2, where one of the 2-thienyl rings has been opened, has been fully characterized and shown to be derived from a ring-opened mu-vinylidene intermediate W-2(O(t)Bu)(4)(mu-CCHCHCHS)(sigma-2-Tn). Rather interestingly, the compound W-2(sigma-2-Th)(NMe(2))(5) reacts with (t)BuOH to give only W-2(2-Th)(O(t)Bu)(5) and HNMe(2). Reactions between 1 and the less sterically demanding alcohols (PrOH)-Pr-i and (t)BuCH(2)OH lead to W-2(OR)(6) compounds with liberation of HNMe(2) and the sulfur containing hydrocarbon. Compound 1 (M = W, 2-Th) reacts with CO2 to give W-2(NMe(2))(2)(O-2(NMe(2))(2)(sigma 2-Th)(2), 3, while with pivalic anhydride W-2(O(2)C(t)Bu)(4) is formed via reductive elimination of the C-C coupled product 2,2'-bithiophene and (t)BuCONMe(2) (4 equiv). 1 (M = W, 2-Th) and CO yield a product formulated as W-2(NMe(2))(4)(mu-CCHCHCHS)(sigma-2-Th)(CO)(3) wherein one ring has opened to form a mu-vinylidene thiolate Ligand. Attempts to prepare 1,2-W(2)L(2)(NMe(2))(4) compounds are described where L = an eta(1)- nitrogen containing heterocycle but only for L = 2-methylindolyl was a compound successfully characterized, Reactions of these compounds with (t)BuOH gave W-2(O(t)Bu)(6) and LH (2 equiv). The compound W-2(sigma-2-FU)(2)(NMe(2))(4) was prepared and characterized (2-Fu = 2-furyl) and shown to undergo ring-opening in its reaction with (t)BuOH to give W-2(O(t)Bu)(5)(mu u-CCH2CHCHO) (sigma-2-Fu), 4, in an analogous manner to the 2-Th complex. The complexes 1 (M = W, 2-Th), 2, 3, and 4 have been characterized by single crystal X-ray studies. The results described herein are compared to other ring-opening reactions of S, N, and O organic heterocyclic compounds as models for the activation of S, N, and O containing fossil fuels in hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and hydrodeoxygenation (HDO) processes. The cleavage of the C-X bonds at the (M=M)(6+) centers (M = Mo, W and X = S, N and O) is also compared with earlier cleavage reactions involving C=O, RC=N, R(2)C=O, and Ar2C=S compounds.

  DOI：

  10.1021/ja962978v

文献信息

• A study of the photochemical reaction between W2(OCH2 tBu) 6P4. Characterization of the phosphidocluster W4 (P) 2 (OCH2 tBu) 10
  作者：Malcolm H. Chisholm、Kristen Folting、Manfred Scheer

  DOI：10.1016/s0277-5387(98)00079-5

  日期：1998.8

  reaction between W2 (OCH2tBu) 6 and P4 has been studied by NMRspectroscopy in toluene-d8 and those reactions have been complemented by studies on the benchtop. A complex sequence of reactions is implicated by the formation of a variety of products, oneof which has been observed previously in the thermal reaction between W2 (OCH2tBu) 6L2 whereL = py and HNMe2 and P4, namely W3 (μ3-P) (OCH2tBu) 9, while others

  W 2（OCH 2 t Bu）6和P 4之间的光化学反应已通过NMR光谱法在甲苯d 8中进行了研究，而这些反应已在台式研究中得到了补充。反应的复杂过程涉及多种产物的形成，其中一种产物先前已在W 2（OCH 2 t Bu）6 L 2（其中L = py和HNMe 2和P 4，即W ）之间的热反应中观察到3（μ 3 -P）（OCH 2吨丁基）9，而其他必须来自OR配体的降解。一种新的化合物W 4（μ 3 -P）2（μ -OCH 2吨丁基）4（OCH 2吨丁基）6已经beenisolated和表征。在−165°C时的晶体数据：a = 19.955（4），b = 25.222（3），c = 12.775（2）Å，Z = 4和空间群P出租车。中心对称结构由金属原子的扭曲菱形组成，金属原子具有两个不同的W-W边缘距离2.6938（8）和2.981（8）Å，并且键合W- W距离之间的主链W原子之间的距离为2
• An Approach to Novel Complexes with a Tungsten−Phosphorus Triple Bond
  作者：Manfred Scheer、Peter Kramkowski、Kay Schuster

  DOI：10.1021/om990019e

  日期：1999.7.1

  complex [W(CO)2(η2-PCAr‘)W(CO)5}2] (7) is formed. The function of [W2(OtBu)6] in this reaction is uncertain, but stoichiometric amounts of [W2(OtBu)6] are essential to obtain complex 6. Reduction of the size of the alkoxide ligands by the use of [W2(ONp)6] (Np = CH2tBu) in the three-component reaction with Ar‘C⋮P leads to the trinuclear cluster compounds [W3〈(μ3-P)W(CO)5}〉(μ-ONp)3(ONp)6] (8) and [W

  [W 2（OtBu）6 ]与tBuC⋮P的复分解反应生成了磷酰基络合物[（tBuO）3 W⋮P]（1），当在酸性路易斯酸存在下进行反应时，该化合物可以稳定下来[M（CO）5 thf]类型的羰基配合物（M = Cr，W）。然而，复分解产物[（tBuO）3 W⋮CtBu]和[（tBuO）3 W⋮P→M（CO）5 ] [M = W（4a），Cr（4b）]与tBuC⋮P的进一步反应在随后的1,3-OtBu转变为金属磷酰基环丁二烯衍生物[（tBuO）2 W C（tBu）} 2 P（OtBu）]（2a）和[（tBuO）2 WC（tBu）P M（CO）5 } P（OtBu）] [M = W（5a），M = Cr（5b）]。为了防止后者，在三组分反应中使用大体积的磷炔烃Ar'C⋮P（Ar'= 2,4,6-tBu 3 C 6 H 2）代替tBuC⋮P。令人惊讶的是，发生了Ar'C“ P的“从头到尾”的二
• Chacon, Stephanie T.; Chisholm, Malcolm H.; Folting, Kirsten, Organometallics, 1991, vol. 10, # 10, p. 3722 - 3735
  作者：Chacon, Stephanie T.、Chisholm, Malcolm H.、Folting, Kirsten、Huffman, John C.、Hampden-Smith, Mark J.

  DOI：——

  日期：——
• Tetranuclear Phosphinidine, Phosphide, Arsenide, and Oxide Anionic Clusters of Molybdenum and Tungsten Supported by Neopentoxide Ligands:  Na(18-crown-6)[M₄(μ₃-PSiMe₃)(OCH₂^tBu)₁₁], K(18-crown-6)[M₄(μ₃-E)(OCH₂^tBu)₁₀] (E = P, As), K(18-crown-6)₂[Mo₄(μ₃-O)(OCH₂^tBu)₁₁]
  作者：Theodore A. Budzichowski、Malcolm H. Chisholm、Kirsten Folting、William E. Streib、Manfred Scheer

  DOI：10.1021/ic951292l

  日期：1996.1.1

  From the reactions between M(2)(OCH(2)(t)Bu)(6) (2 equiv) and NaP(SiMe(3))(2) (1 equiv) in benzene and 18-crown-6 the phosphinidine clusters [M(4)(mu(3)-PSiMe(3))(OCH(2)(t)Bu)(11)](-), compounds 1 (M = Mo) and 2 (M = W) are formed and are reactive intermediates in the formation of [M(4)(mu(3)-P)(OCH(2)(t)Bu)(10)](-) cluster anions, compounds 3 (M = Mo) and 4 (M = W), respectively, which have been isolated and characterized as their Na(18-crown-6)(+) salts. Crystals of Na(18-crown-6)(+)[Mo-4(mu(3)-P)(OCH(2)(t)Bu)(10)](-). C6H6 were examined by single crystal X-ray crystallography at -110 degrees C in the space group Pn with a 13.000(2) Angstrom, b = 17.501(3) Angstrom, c = 18.703(2) Angstrom, and beta = 93.11(1)degrees with Z = 2 and at -173 degrees C in the space group Cc with a = 22.118(4) Angstrom, b = 17.480(3) Angstrom, c = 23.250(4) Angstrom, and beta = 110.82(1)degrees with Z = 4. At the lower temperature, there is higher symmetry and no disorder of the 18-crown-6 molecule. The cluster anion has a Mo-4 butterfly with a mu(3)-P ligand and virtual mirror symmetry. One wing-tip Mo atom is five-coordinate and bonded to the mu(3)-P atom and shows longer Mo-to-Mo distances (2.68(1) and 2.71(1) Angstrom) relative to its counterpart (2.48(1) and 2.50(1) Angstrom); the backbone Mo-Mo distance is 2.53(1) Angstrom. The cluster anion in 3 but not 4 is also accessible from the reaction between Mo-2(OCH(2)(t)Bu)(6) (2 equiv), PH3, and KOCH(2)(t)Bu (1 equiv) in THF/18-crown-6 (THF = tetrahydrofuran). A similar approach involving AsH3, Mo-2(OCH(2)(t)Bu)(6), and KOCH(2)(t)Bu gave the mu(3)-arsenide cluster complex K(18-crown-6)(+)[Mo-4(mu(3)-As)(OCH(2)(t)Bu)(10)](-), compound 5, which by NMR spectroscopy is analogous in structure to 3. The reaction between Mo-2(OCH(2)(t)Bu)(6) (2 equiv) and KOH in THF/18-crown-6 gave K(18-crown-6)(2)(+)[Mo-4(mu(3)-O)(OCH(2)(t)Bu)(11)](-), compound 6, which is proposed to be isostructural with the phosphinidine complexes 1 and 2 on the basis of NMR data. Crystal data for K(eta(6)-C12H24O6)(eta(2)-C12H24O6)(+)[Mo-4(mu(3)-O)(OCH(2)(t)Bu)(11)](-) at -165 degrees C: a 17.595(2) Angstrom, b = 28.044(3) Angstrom, c = 20.443(2) Angstrom, beta = 97.61(1)degrees with Z = 4, and space group P2(1)/n. The cluster anion in 6 contains a 12-electron Mo-4 butterfly with 12 M-M bonding electrons, as in 3, but the shortest Mo-Mo distance 2.42(1) Angstrom involves the backbone metal atoms. The Mo-Mo distances involving the ore-capped triangle (2.61(1) and 2.62(1) Angstrom) are notably longer than those in the other triangle (2.48(1) Angstrom).
• Budzichowski; Chisholm; Folting, Journal of the American Chemical Society, 1995, vol. 117, # 28, p. 7428 - 7440
  作者：Budzichowski、Chisholm、Folting、Huffman、Streib

  DOI：——

  日期：——