trans-bis-sulfido-tetrakis-trimethylphosphine-tungsten(IV) | 135456-92-7

• 分子结构分类: 有机化合物 - 有机金属化合物
• 英文名称: trans-bis-sulfido-tetrakis-trimethylphosphine-tungsten(IV)
• 英文别名: bis(sulfanylidene)tungsten;trimethylphosphane
• CAS: 135456-92-7
• 化学式: C₁₂H₃₆P₄S₂W
• 分子量: 552.295
• InChiKey: PRSLJACWDHIBDJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.72
• 重原子数：
  19.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  trans-bis-sulfido-tetrakis-trimethylphosphine-tungsten(IV) 、 乙醛 以 苯 为溶剂， 以56%的产率得到W(PMe3)2(S)2(η(2)-OCHMe)
  参考文献：
  名称：

  Terminal Sulfido, Selenido, and Tellurido Complexes of Tungsten

  摘要：

  The terminal chalcogenido complexes trans-W(PMe(3))(4)(E)(2) (E = S, Se, Te) have been synthesized by the reactions of W(PMe(3))(4)(eta(2)-CH(2)PMe(2))H With H(2)E (E = S, Se) and elemental Te. W(PMe(3))(4)(Te)(2) is the first example of a transition-metal complex containing a terminal tellurido ligand. Each of the chalcogenido complexes W(PMe(3))4(E)2 reacts reversibly with RCHO to yield the eta(2)-aldehyde derivatives W(PMe(3))(2)(E)(2)(eta(2)-OCHR), although the equilibrium constants vary strongly as a function of the chalcogen, with Ks much greater than Ks, > KTe The Phle3 ligands of W(PMe3)4(S)2 and W(PMe(3))(4)(Te)(2) are readily displaced by Bu(t)NC to give W(PMe(3))(2)(CNBUt)(2)(E)(2). In marked contrast, however, the corresponding reaction of the tellurido derivative W(PMe(3))(4)(Te)(2) with Bu(t)NC results in the unprecedented coupling of the two terminal tellurido ligands, leading to the formation of the eta(2)-ditellurido derivative W(PMe(3))(CNBu(t))(4)(eta(2)-Te-2). Structural and bonding aspects of the terminal chalcogenido complexes have been probed by X-ray diffraction, while Se-77 and Te-125 NMR spectroscopies have identified a linear correlation between Se-77 and Te-125 NMR chemical shifts for structurally analogous selenido and tellurido complexes. W(PMe(3))(4)(S)(2) is monoclinic, P2/n (No. 13), a = 15.914(2) Angstrom, b = 9.682(2) Angstrom, c = 15.926(3) Angstrom, beta = 111.92(2)degrees, Z = 4. W(PMe(3))(4)(Se)(2) is monoclinic, P2/n (No. 13), a = 16.040(5) Angstrom, b = 9.738(2) Angstrom, c = 16.096(3) Angstrom, beta = 113.27(2)degrees, Z = 4, W(PMe(3))(4)(Te)(2) is tetragonal, I<(4)over bar2m> (No. 121), a = b = 9.717(1) Angstrom, c = 12.360(2) Angstrom, Z = 2. W(PMe(3))(4)(Se)H-2 is monoclinic, Cc (No. 9), a = 9.580(2) Angstrom, b = 15.757(3) Angstrom, c = 14.860(3) Angstrom, beta = 98.54(2)degrees, Z = 4. W(PMe(3))(2)(CNBu(t))(2)(S)(2) is monoclinic, P2(1)/n (No. 14), a = 11.003(2) Angstrom, b = 10.513(3) Angstrom, c = 11.947(3) Angstrom, beta = 109.87(2)degrees, Z = 2. W(PMe(3))(2)(CNBu(t))(2)(Se)(2) is monoclinic, P2(1)/n (No. 14), a = 11.147(5) Angstrom, b = 10.617(5) Angstrom, c = 11.973(4) Angstrom, beta = 110.16(3)degrees, Z = 2. W(PMe(3))(2)(Te)(2)(eta(2)-OCH2) is orthorhombic, Pnma (No. 62), a = 10.441(3) Angstrom, b = 11.299(4) Angstrom, c = 13.812(4) Angstrom, Z = 4. W(PMe(3))(2)(S)(2)(eta(2)-OCHPh) is monoclinic, P2(1)/c (No. 14), a 12.561(3) A, b = 8.684(1) Angstrom, c = 18.182(3) Angstrom, beta = 108.57(2)degrees, Z = 4. W(PMe(3))(2)(Se)(2)(eta(2)-OCHPh) is monoclinic, P2(1)/c (No. 14), a = 12.563(5) Angstrom, b = 8.731(4) Angstrom, c = 18.461(6) Angstrom, beta = 109.22(3)degrees, Z = 4. W(PMe(3))(2)(Te)(2)(eta(2)-OCHPh) is monoclinic, P2(1)/n (No. 14), a = 12.661(2) Angstrom, b = 8.931(1) Angstrom, c = 18.779(4) Angstrom, beta = 108.47(2)degrees, Z = 4. W(PMe(3))(CNBu(t))(4)(eta(2)-Te-2) is orthorhombic, Pbca (No. 61), a = 18.097(4) Angstrom, b = 18.978(2) Angstrom, c = 19.741(3) Angstrom, Z = 8.

  DOI：

  10.1021/ic00129a021
• 作为产物：
  描述：

  bis-hydrido-bis-hydrosulfido-tetrakis-trimethylphosphine-tungsten(IV) 以 苯 为溶剂， 以97%的产率得到trans-bis-sulfido-tetrakis-trimethylphosphine-tungsten(IV)
  参考文献：
  名称：

  Terminal Sulfido, Selenido, and Tellurido Complexes of Tungsten

  摘要：

  The terminal chalcogenido complexes trans-W(PMe(3))(4)(E)(2) (E = S, Se, Te) have been synthesized by the reactions of W(PMe(3))(4)(eta(2)-CH(2)PMe(2))H With H(2)E (E = S, Se) and elemental Te. W(PMe(3))(4)(Te)(2) is the first example of a transition-metal complex containing a terminal tellurido ligand. Each of the chalcogenido complexes W(PMe(3))4(E)2 reacts reversibly with RCHO to yield the eta(2)-aldehyde derivatives W(PMe(3))(2)(E)(2)(eta(2)-OCHR), although the equilibrium constants vary strongly as a function of the chalcogen, with Ks much greater than Ks, > KTe The Phle3 ligands of W(PMe3)4(S)2 and W(PMe(3))(4)(Te)(2) are readily displaced by Bu(t)NC to give W(PMe(3))(2)(CNBUt)(2)(E)(2). In marked contrast, however, the corresponding reaction of the tellurido derivative W(PMe(3))(4)(Te)(2) with Bu(t)NC results in the unprecedented coupling of the two terminal tellurido ligands, leading to the formation of the eta(2)-ditellurido derivative W(PMe(3))(CNBu(t))(4)(eta(2)-Te-2). Structural and bonding aspects of the terminal chalcogenido complexes have been probed by X-ray diffraction, while Se-77 and Te-125 NMR spectroscopies have identified a linear correlation between Se-77 and Te-125 NMR chemical shifts for structurally analogous selenido and tellurido complexes. W(PMe(3))(4)(S)(2) is monoclinic, P2/n (No. 13), a = 15.914(2) Angstrom, b = 9.682(2) Angstrom, c = 15.926(3) Angstrom, beta = 111.92(2)degrees, Z = 4. W(PMe(3))(4)(Se)(2) is monoclinic, P2/n (No. 13), a = 16.040(5) Angstrom, b = 9.738(2) Angstrom, c = 16.096(3) Angstrom, beta = 113.27(2)degrees, Z = 4, W(PMe(3))(4)(Te)(2) is tetragonal, I<(4)over bar2m> (No. 121), a = b = 9.717(1) Angstrom, c = 12.360(2) Angstrom, Z = 2. W(PMe(3))(4)(Se)H-2 is monoclinic, Cc (No. 9), a = 9.580(2) Angstrom, b = 15.757(3) Angstrom, c = 14.860(3) Angstrom, beta = 98.54(2)degrees, Z = 4. W(PMe(3))(2)(CNBu(t))(2)(S)(2) is monoclinic, P2(1)/n (No. 14), a = 11.003(2) Angstrom, b = 10.513(3) Angstrom, c = 11.947(3) Angstrom, beta = 109.87(2)degrees, Z = 2. W(PMe(3))(2)(CNBu(t))(2)(Se)(2) is monoclinic, P2(1)/n (No. 14), a = 11.147(5) Angstrom, b = 10.617(5) Angstrom, c = 11.973(4) Angstrom, beta = 110.16(3)degrees, Z = 2. W(PMe(3))(2)(Te)(2)(eta(2)-OCH2) is orthorhombic, Pnma (No. 62), a = 10.441(3) Angstrom, b = 11.299(4) Angstrom, c = 13.812(4) Angstrom, Z = 4. W(PMe(3))(2)(S)(2)(eta(2)-OCHPh) is monoclinic, P2(1)/c (No. 14), a 12.561(3) A, b = 8.684(1) Angstrom, c = 18.182(3) Angstrom, beta = 108.57(2)degrees, Z = 4. W(PMe(3))(2)(Se)(2)(eta(2)-OCHPh) is monoclinic, P2(1)/c (No. 14), a = 12.563(5) Angstrom, b = 8.731(4) Angstrom, c = 18.461(6) Angstrom, beta = 109.22(3)degrees, Z = 4. W(PMe(3))(2)(Te)(2)(eta(2)-OCHPh) is monoclinic, P2(1)/n (No. 14), a = 12.661(2) Angstrom, b = 8.931(1) Angstrom, c = 18.779(4) Angstrom, beta = 108.47(2)degrees, Z = 4. W(PMe(3))(CNBu(t))(4)(eta(2)-Te-2) is orthorhombic, Pbca (No. 61), a = 18.097(4) Angstrom, b = 18.978(2) Angstrom, c = 19.741(3) Angstrom, Z = 8.

  DOI：

  10.1021/ic00129a021

文献信息

• Aggregation of PMe₃-Stabilized Molybdenum Sulfides and the Catalytic Dehydrogenation of H₂S
  作者：Daniel E. Schwarz、Thomas B. Rauchfuss、Scott R. Wilson

  DOI：10.1021/ic026215m

  日期：2003.4.1

  The reactivity Of [MoS4](2-) (1) toward PMe3 was explored in the presence and absence of proton donors. Whereas MeCN solutions of (Et4N)(2)[MoS4] and PMe3 are stable, in the presence of H2S such solutions catalyze formation of H-2 and SPMe3. Addition of NH4+ to such solutions afforded MoS2(PMe3)(4) (2), which can be prepared directly from (NH4)(2)[1]. Compound 2 is reactive toward thiols via a process proposed to involve the initial dissociation of one PMe3 ligand, a hypothesis supported by the relative inertness of trans-MoS2(dmpe)(2). Benzene solutions of 2 react with EtSH to give Mo-2(mu-S)(mu-SH)(PMe3)(4)(SEt)(3) (3Et). Analogous reactions with thiocresol (MeC6H4SH) and H2S gave Mo-2(mu-S)(mu-SH)(PMe3)(4)(SR)(3) (R = tol, H). Crystallographic analyses of 3Et, 3H, and 3tol indicate dinuclear species with seven terminal ligands and a Mo-2(mu-SR)(mu-S) core (r(Mo-Mo) = 2.748(1) Angstrom). From reaction mixtures leading to 3Et from 2, we obtained the intermediate Mo-2(IV)(mu-S)(2)(SEt)(4)(PMe3)(2) (4), an edge-shared bis(trigonal pyramidal) structure. Compounds 3H and 3Et react further with H2S to give Mo-4(mu(2)-S)4(mu(3)-S)(2)(PMe3)(6)(SH)(2) (5H) and o(0)4(mu(2)-S)(4)(mu(3)-S)(2)(PMe3)(6)(SEt)(2) (5Et), respectively. Analogously, W-4(mu(2)-S)(4)(mu(3)-S)(2)(PMe3)(6)(SH)(2) was synthesized from a methanol solution of (NH4)(2)WS4 With H2S and PMe3. A highly accurate crystallographic analysis of (NH4)(2)MoS4 (R-1 = 0.0193) indicates several weak NH...S interactions.
• Rabinovich, Daniel; Parkin, Gerard, Journal of the American Chemical Society, 1991, vol. 113, # 15, p. 5904 - 5905
  作者：Rabinovich, Daniel、Parkin, Gerard

  DOI：——

  日期：——