Discrete Mononuclear and Dinuclear Nickel(II) Complexes of Alkane- and Areneselenolates: Syntheses, Structures, and Properties of (Et4N)2[Ni2(Se(CH2)3<
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- 作者：Christine Marganian Goldman ; Marilyn M. Olmstead ; and Pradip K. Mascharak
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：May 8, 1996
- 年：1996
- 卷：35
- 期：10
- 页码：2752 - 2757
- 全文大小：235K
- 年卷期：v.35,no.10(May 8, 1996)
- ISSN：1520-510X
文摘
Reaction of the alkanediselenolate(Et4N)2(Se(CH2)3Se)with NiCl2·6H2O in ethanol/acetonitrilemixture affordsthe dimeric complex(Et4N)2[Ni2(Se(CH2)3Se)3](1), in which the coordination geometry around eachNi(II) centeris square planar. In contrast, reaction of the areneselenolatePhSe- with NiCl2·6H2O inacetonitrile gives rise to(Ph4P)2[Ni(SePh)4](2), which comprises a distorted tetrahedralNiSe4 chromophore. When the bulkyareneselenolate2,4,6-(Me)3C6H2Se-is used, the same reaction affords the dimeric complex(Ph4P)2[Ni2(
-2,4,6-(Me)3C6H2Se)2(2,4,6-(Me)3C6H2Se)4]·8CH3CN(3), which contains square planar NiSe4chromophores. Unfavorable stericinteractions among o-methyl groups, nickel, and the Se atomsdo not allow a tetrahedral coordination spherearound nickel in 3. Complex 1 crystallizesin the orthorhombic space group Pna21 witha = 16.645(3) Å, b =20.214(6) Å, c = 11.428(3) Å, V =3846(3) Å3, and Z = 4. Thestructure of 1 was refined to R = 7.34% onthebasis of 1694 (I > 4
(I)) data.Complex 2 crystallizes in the orthorhombic space groupPca21 with a =17.617(7)Å, b = 13.758(5) Å, c =24.776(11) Å, V = 6005(4) Å3, andZ = 4. The structure of 2 was refined toR =6.45% on the basis of 4034 (I > 4(I))data. Complex 3 crystallizes in the triclinic spacegroup P
with a =14.443(3) Å, b = 14.751(3) Å, c =15.351(3) Å, 
= 75.66(3)
, 
= 71.09(3),
= 65.18(3), V = 2784.4(10)Å3, and Z = 1. The structure of3 was refined to R = 7.34% on the basis of7236 (I > 4(I)) data. TheseNi(II)selenolate complexes are sensitive to oxygen, and their formation ishindered by the presence of water in thereaction mixture. The average Ni-Se bond lengths in all thehomoleptic square planar selenolates are shorterthan the average Ni-Se bond length in the tetrahedral complex[Ni(SePh)4]2-.
-2,4,6-(Me)3C6H2Se)2(2,4,6-(Me)3C6H2Se)4]·8CH3CN(3), which contains square planar NiSe4chromophores. Unfavorable stericinteractions among o-methyl groups, nickel, and the Se atomsdo not allow a tetrahedral coordination spherearound nickel in 3. Complex 1 crystallizesin the orthorhombic space group Pna21 witha = 16.645(3) Å, b =20.214(6) Å, c = 11.428(3) Å, V =3846(3) Å3, and Z = 4. Thestructure of 1 was refined to R = 7.34% onthebasis of 1694 (I > 4(I)) data.Complex 2 crystallizes in the orthorhombic space groupPca21 with a =17.617(7)Å, b = 13.758(5) Å, c =24.776(11) Å, V = 6005(4) Å3, andZ = 4. The structure of 2 was refined toR =6.45% on the basis of 4034 (I > 4(I))data. Complex 3 crystallizes in the triclinic spacegroup P with a =14.443(3) Å, b = 14.751(3) Å, c =15.351(3) Å, = 75.66(3), = 71.09(3), = 65.18(3), V = 2784.4(10)Å3, and Z = 1. The structure of3 was refined to R = 7.34% on the basis of7236 (I > 4(I)) data. TheseNi(II)selenolate complexes are sensitive to oxygen, and their formation ishindered by the presence of water in thereaction mixture. The average Ni-Se bond lengths in all thehomoleptic square planar selenolates are shorterthan the average Ni-Se bond length in the tetrahedral complex[Ni(SePh)4]2-.