STUDIES OF THE REACTIVITY OF BINARY THIOMOLYBDATES AND TERTIARY OXOTHIOMOLYBDATES TOWARD ELECTROPHILES - REACTIONS WITH DICARBOMETHOXYACETYLENE AND THE SYNTHESIS AND STRUCTURES OF THE [ET4N]2[MOO(L)2], ANTI-[ET4N]2[MO2O2S2(L)2], SYN-[PH4P]2[MO2O2S2(L)2].2DMF, [PH4P]2[MO(L)3].DMF.C6H6, AND [PH4P]2[MO2S2(L)4].2CH2CL2 COMPLEXES (L = 1,2-DICARBOMETHOXY-1,2-ETHYLENEDITHIOLATE)
STUDIES OF THE REACTIVITY OF BINARY THIOMOLYBDATES AND TERTIARY OXOTHIOMOLYBDATES TOWARD ELECTROPHILES - REACTIONS WITH DICARBOMETHOXYACETYLENE AND THE SYNTHESIS AND STRUCTURES OF THE [ET4N]2[MOO(L)2], ANTI-[ET4N]2[MO2O2S2(L)2], SYN-[PH4P]2[MO2O2S2(L)2].2DMF, [PH4P]2[MO(L)3].DMF.C6H6, AND [PH4P]2[MO2S2(L)4].2CH2CL2 COMPLEXES (L = 1,2-DICARBOMETHOXY-1,2-ETHYLENEDITHIOLATE)
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DOI：
10.1021/ic00004a028
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发表时间：
1991-02-20
影响因子：
4.6
通讯作者：
SALIFOGLOU, A
中科院分区：
文献类型：
--
作者：
COUCOUVANIS, D;HADJIKYRIACOU, A;SALIFOGLOU, A
本文描述了各种硫代或硫代钼酸盐与活化炔二甲氧基乙炔的反应。反磁性的[Et4N]2[MoO(L)2](I)，反[Et4N]2[Mo2O2S2(L)2](II)，SYN-[Ph4P]2[Mo2O2S2(L)2]2DMF(III)，[Ph4P]2[Mo(L)3].DMF.C6H6(IV)，[Ph4P]2[Mo2S2(L)4].2CH2Cl2(V)的合成是在DMA(Et4N)2[MoO(S4)2]，(L=1，2-二甲甲氧基-1，2-二硫代乙二酸乙酯，AD)的反应中完成的(Et4N)2[Mo2O2S9]，(Ph4P)2-[Mo2OS7]，(Ph4P)2[MoS(S4)2]和(Ph4P)2[Mo2S10/S12]。这些反应是通过DMA对Mo=S或Mo-S2的亲电攻击，然后将DMA插入到这些发色团中而进行的。不稳定的乙烯基硫化物或乙烯基二硫化物中间体通过热或硫催化的途径转化为最终的二硫烯产品。化合物I-V分别以P2(1)/c、P1bar、P1bar、C2/c和P1bar空间群结晶。单元尺寸为a=100.5(4)埃，b=9.979(2)埃，c=21.363(4)埃，β=100.5(2)度，对于I，a=9.004(2)埃，b=8.975(3)埃，c=13.904(2)埃，α=90.53(2)度，β=102.04(1)度，和伽马=12.919(2)度，B=14.863(6)埃，c=18.844(6)埃，α=95.86(3)度，β=102.61(2)度，伽马=93.74(3)度，对于III，a=22.907(14)埃，b=14.619(9)埃，c=43.746(21)埃，以及β=95.34(5)度，以及a=12.778(2)埃，b=13.616(3)埃，c=13.898(3)埃，对于V，α=105.62(2)度，β=98.80(1)度，伽马=110.10(1)。所有结构的数据都是在使用MoK-α辐射的自动衍射仪上获得的。I的2704个数据上的393个参数、II的1774个数据上的217个参数、III的6350个数据上的775个参数、IV的2637个数据上的389个参数和V的2412个数据上的313个参数的全矩阵精化分别给出了最终的R(W)值0.050、0.024、0.044、0.077和0.066。I的结构表明Mo(IV)(O)(S4)核单元(Mo=O=1.686(6)埃；Mo-S(Eq)=2.380(4)埃)的赤道平面上有一个末端氧代配体和两个双齿DMA配体配位。II和III中的反和正[Mo2O2(Mu-2-S)2]2+单元分别具有理想化的C2H和C2-nu几何构型。每个单元由两个DMAD双齿配体配位。Mo(V)(O)(S4)亚基为扭曲的四方锥体结构，末端为氧代配体，DMAD和Mu-2-S配体占据赤道面。相邻的金字塔共有桥联的S配体作为赤道上的共同中心(对于II，Mo-Mo=2.904(1)埃，Mo=O=1.684(2)埃，Mo-S(B)=2.328埃，Mo-S(L)=2.419埃，Mo-S(B)-Mo=77.13(1)度，S(B)-Mo-S(B)=2.419埃；对Ⅲ，Mo-Mo=2.853(1)埃，Mo=O=1.675(2)埃，Mo-S(B)=2.331(3)埃，Mo-S(L)=2.425(8)埃，Mo-S(B)-Mo=75.51(1)度，和S(B)-Mo-S(B)=100.9(1)度)。IV的结构为Mo(IV)由三个双齿DMAD配体配位，并含有轻微扭曲的三棱柱[Mo(IV)(S)6]核(Mo-S(L)=2.393埃)。V中中心对称阴离子的结构包含两个共享边的扭曲的八面体单元[Mo(V)(S)6]，它们共享桥联的S配体。这些亚基中的Mo(V)除了两个桥联硫化物外，还被两个双齿DMAD配体配位(Mo-Mo=2.938埃，Mo-S(B)=2.321埃，Mo-S(L)=2.383，2.459埃；Mo-S(B)-Mo=78.6(1)度，S(B)-Mo-S(B)=2.383(1)度)。V中不同的Mo-S(L)键归因于桥联配体的显著反式作用。讨论了这些配合物的光谱和电化学性质，并讨论了各种钼中心官能团的反应特性。
The reactions of various thio- or oxothiomolybdates with the activated alkyne dicarbomethoxyacetylene, DMA, are described. The syntheses of the diamagnetic [Et4N]2[MoO(L)2] (I), anti-[Et4N]2[Mo2O2S2(L)2] (II), syn-[Ph4P]2[Mo2O2S2(L)2].2DMF (III), [Ph4P]2[Mo(L)3].DMF.C6H6 (IV), and [Ph4P]2[Mo2S2(L)4].2CH2Cl2 (V) complexes (L = 1,2-dicarbomethoxy-1,2-ethylenedithiolate, DMAD) are accomplished in reactions of DMA with (Et4N)2[MoO(S4)2], (Et4N)2[Mo2O2S9], (Ph4P)2-[Mo2OS7], (Ph4P)2[MoS(S4)2], and (Ph4P)2[Mo2S10/S12], respectively. It is proposed that these reactions proceed by electrophilic attack of DMA on either Mo = S or Mo-S2 with subsequent DMA insertion into these chromophores. The unstable vinyl sulfide or vinyl disulfide intermediates are converted to the final dithiolene products either thermally or by a sulfur-catalyzed pathway. The compounds I-V crystalize in the space groups P2(1)/c, P1BAR, P1BAR, C2/c, and P1BAR, respectively. The cell dimensions are a = 17.664 (4) angstrom, b = 9.979 (2) angstrom, c = 21.363 (4) angstrom, and beta = 100.5 (2)-degrees for I, a = 9.004 (2) angstrom, b = 8.975 (3) angstrom, c = 13.904 (2) angstrom, alpha = 90.53 (2)-degrees, beta = 102.04 (1)-degrees, and gamma = 112.11 (2)-degrees for II, a = 12.919 (4) angstrom, b = 14.863 (6) angstrom, c = 18.844 (6) angstrom, alpha = 95.86 (3)-degrees, beta = 102.61 (2)-degrees, and gamma = 93.74 (3)-degrees for III, a = 22.907 (14) angstrom, b = 14.619 (9) angstrom, c = 43.746 (21) angstrom, and beta = 95.34 (5)-degrees for IV, and a = 12.778 (2) angstrom, b = 13.616 (3) angstrom, c = 13.898 (3) angstrom, alpha = 105.62 (2)-degrees, beta = 98.80 (1)-degrees, and gamma = 110.10 (1) for V. The data for all structures were obtained on an automatic diffractometer employing Mo K-alpha radiation. Full-matrix refinement of 393 parameters on 2704 data for I, 217 parameters on 1774 data for II, 775 parameters on 6350 data for III, 389 parameters on 2637 data for IV, and 313 parameters on 2412 data for V gave final R(w) values of 0.050, 0.024, 0.044, 0.077, and 0.066, respectively. The structure of I shows the Mo(IV) coordinated by a terminal oxo ligand and two bidentate DMA ligands in the equatorial plane of the distorted square-pyramidal Mo(IV)(O)(S4) core unit (Mo = O = 1.686 (6) angstrom; Mo-S(eq) = 2.380 (4) angstrom). The structures of the anti- and syn-[Mo2O2(mu-2-S)2]2+ units in II and III have idealized C2h and C2-nu geometry, respectively. Each unit is coordinated by two DMAD bidentate ligands. The Mo(V)(O)(S4) subunits are distorted square pyramidal with a terminal oxo ligand and the DMAD and mu-2-S ligands occupying the equatorial planes. Adjacent pyramids share the bridging S ligands as common equatorial sites (for II, Mo-Mo = 2.904 (1) angstrom, Mo = O = 1.684 (2) angstrom, Mo-S(b) = 2.328 angstrom, Mo-S(L) = 2.419 angstrom, Mo-S(b)-Mo = 77.13 (1)-degrees, and S(b)-Mo-S(b) = 102.91 (1)-degrees; for III, Mo-Mo = 2.853 (1) angstrom, Mo = O = 1.675 (2) angstrom, Mo-S(b) = 2.331 (3) angstrom, Mo-S(L) = 2.425 (8) angstrom, Mo-S(b)-Mo = 75.5 (1)-degrees, and S(b)-Mo-S(b) = 100.9 (1)-degrees).The structure of IV shows the Mo(IV) coordinated by three bidentate DMAD ligands and contains the slightly distorted trigonal prismatic [Mo(IV)(S)6] core (Mo-S(L) = 2.393 angstrom). The structure of the centrosymmetric anion in V contains two edge-sharing distorted octahedral [Mo(V)(S)6] units that share the bridging S ligands. The Mo(V) in each of these subunits, in addition to the two bridging sulfides, is coordinated by two bidentate DMAD ligands (Mo-Mo = 2.938 angstrom, Mo-S(b) = 2.321 angstrom, Mo-S(L) = 2.383, 2.459 angstrom; Mo-S(b)-Mo = 78.6 (1)-degrees, S(b)-Mo-S(b) = 101.4 (1)-degrees). The different Mo-S(L) bonds in V are attributed to a significant trans effect of the bridging ligands. The spectroscopic and electrochemical properties of these complexes as well as a discussion of the reactivity characteristics of the various Mo-centered functional groups are discussed.