NiN(2)S(2) complexes as metallodithiolate ligands to Rh(I), Rh(II) and Rh(III).
NiN(2)S(2) complexes as metallodithiolate ligands to Rh(I), Rh(II) and Rh(III).
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NiN(2)S(2) 作为金属二硫醇盐配体与 Rh(I)、Rh(II) 和 Rh(III) 形成络合物。
DOI：
10.1039/b605768c
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发表时间：
2006
期刊：
影响因子：
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通讯作者：
Darensbourg,MarcettaY
中科院分区：
文献类型：
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作者：
Jeffery,StephenP;Green,KaylaN;Rampersad,MarilynV;Reibenspies,JosephH;Darensbourg,MarcettaY
报道了三种分子结构，它们利用NiN 2S 2配体Ni-1，（双（巯基乙基）二氮杂环辛烷）镍和Ni-1′，双（巯基乙基）二氮杂环庚烷）镍作为金属二硫醇盐配体与氧化态I、II和III的铑配位。对于RhI络合物，NiN 2S 2单元表现为与正方形平面RhI（CO）（PPh 3）+部分的双齿配体，其具有115°的铰链或二面角（定义为NiN 2S 2和S2 Rh（C）（P）平面的交叉）。在Ni-1′配体的支持下，RhII氧化态出现在二铑C4桨轮络合物中，其中四个NiN 2S 2单元作为二齿桥连配体与两个单键RhII离子以2.893（8）π的距离连接。本文给出了以NiN_2S_2配合物为桨轮配合物的M-M距离的显著范围。RhIII状态被发现为四金属[Rh（Ni-1′）3]3+簇，大致形状像船螺旋桨，结构类似于三（联吡啶）金属络合物。
Three molecular structures are reported which utilize the NiN2S2 ligands Ni-1, (bis(mercaptoethyl)diazacyclooctane)nickel and Ni-1′, bis(mercaptoethyl)diazacycloheptane)nickel, as metallodithiolate ligands to rhodium in oxidation states I, II and III. For the RhI complex, the NiN2S2 unit behaves as a bidentate ligand to a square planar RhI(CO)(PPh3)+ moiety with a hinge or dihedral angle (defined as the intersection of NiN2S2 and S2Rh(C)(P) planes) of 115°. Supported by Ni-1′ ligands, the RhII oxidation state occurs in a dirhodium C4 paddlewheel complex wherein four NiN2S2 units serve as bidentate bridging ligands to two singly-bonded RhII ions at 2.893(8) Å apart. A compilation of the remarkable range of M–M distances in paddlewheel complexes which use NiN2S2 complexes as paddles is presented. The RhIII state is found as a tetrametallic [Rh(Ni-1′)3]3+ cluster, roughly shaped like a boat propeller and structurally similar to tris(bipyridine)metal complexes.