Trithiotungsten(VI) complexes having phosphine-thiolate hybrid ligands:: Synthesis and cluster forming reactions with CuBr, FeCl2, and [Fe(CH3CN)6](ClO4)2
Trithiotungsten(VI) complexes having phosphine-thiolate hybrid ligands:: Synthesis and cluster forming reactions with CuBr, FeCl2, and [Fe(CH3CN)6](ClO4)2
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DOI：
10.1021/ic010921q
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发表时间：
2002-02-11
影响因子：
4.6
通讯作者：
Tatsumi, K
中科院分区：
文献类型：
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作者：
Arikawa, Y;Kawaguchi, H;Tatsumi, K
在(PPh4)[(Ets)W(S)(3)]的四氢呋喃溶液中加入Hdmsp和Hdpsp，合成了五个三硫钨配合物(PPh4)[(Dmsp)W(S)(3)](1a)和(PPh4)[(Dpsp)W(S)(3)](1b)(R2PCH2CH2S-R=Me(dmsp(-))，Ph(dpsp(-)。在CH3CN中，在PPh3的存在下，CuBr与La反应得到WCu2簇(DMSP)WS3Cu2(PPh3)(2)Br2。La与1当量FeCl2反应生成1：1加合物(PPh4)[(DMSP)WS3(FeCl2)](3)，而3不与过量FeCl2进一步反应。另一方面，3与[Fe(CH3CN)(6)](CIO4)(2)反应生成不寻常的四核簇合物[(DMSP)WS3](2)Fe2Cl(4)，而1a与2当量的[Fe(CH3CN)(6)](CIO4)(2)反应生成环状八核簇合物[(DMSP)WS3Fe](4)(5)。虽然W(VI)、Cu(I)和Fe(II)的氧化态被保留在2和3中，但金属离子在4和5的形成中发生了还原。预计新型的三硫代钨配合物1a和1b将成为各种异金属硫化物簇合物的潜在合成子。
Five-coordinated trithiotungsten complexes (PPh4)[(dMSP)W(S)(3)] (1a) and (PPh4)[(dPSP)W(S)(3)] (1b) (R2PCH2CH2S- R = Me (dmsp(-)), Ph (dpsp(-))) were synthesized by addition of Hdmsp and Hdpsp to a THF solution of (PPh4)[(EtS)W(S)(3)]. Treatment of la with CuBr in the presence of PPh3 in CH3CN afforded a WCU2 cluster (dMSP)WS3CU2(PPh3)(2)Br (2). The reaction of la with 1 equiv of FeCl2 went smoothly to generate a 1:1 adduct (PPh4)[(dMSP)WS3(FeCl2)] (3), while 3 did not react further with excess FeCl2. On the other hand, 3 was found to react with [Fe(CH3CN)(6)](CIO4)(2), giving rise to an unusual tetranuclear cluster, [(dMSP)WS3](2)Fe2Cl (4), while the reaction of 1a with 2 equiv of [Fe(CH3CN)(6)](CIO4)(2) led to a cyclic octanuclear cluster[(dmsp)WS3Fe](4) (5). Although the oxidation states of W(VI), Cu(I), and Fe(II) are retained in 2 and 3, reduction of the metal ions occurs in the formation of 4 and 5. All the complexes reported in this paper were structurally characterized by X-ray analysis. It is anticipated that the new type of trithiotungsten complexes, 1a and 1b, will serve as potential synthons for various heterometallic sulfide clusters.