带有侧链硫醇的单核镍（II）硫醇盐配合物以及通过镍的氧化态和配位配体调节的具有镍……镍相互作用的双核镍（III/II）硫醇盐配合物。

Mononuclear Ni(II)-thiolate complexes with pendant thiol and dinuclear Ni(III/II)-thiolate complexes with Ni...Ni interaction regulated by the oxidation levels of nickels and the coordinated ligands.

作者信息

Lee Chien-Ming, Chiou Tzung-Wen, Chen Hsin-Hung, Chiang Chao-Yi, Kuo Ting-Shen, Liaw Wen-Feng

机构信息

Department of Chemistry, National Tsing Hua University, Hsinchu 30043, Taiwan.

出版信息

Inorg Chem. 2007 Oct 15;46(21):8913-23. doi: 10.1021/ic700719h. Epub 2007 Sep 15.

DOI:10.1021/ic700719h

PMID:17867675

Abstract

Compared to [Ni(II)(SePh)(P(o-C(6)H(3)-3-SiMe(3)-2-S)(2)(o-C(6)H(3)-3-SiMe(3)-2-SH))]- (1a) and [Ni(II)(Cl)(P(o-C(6)H(3)-3-SiMe(3)-2-S)(2)(o-C(6)H(3)-3-SiMe(3)-2-SH))]- (3a) with a combination of the intramolecular [Ni...H-S] and [Ni-S...H-S] interactions, complexes [NiII(SePh)(P(o-C(6)H(3)-3-SiMe(3)-2-S)(2)(o-C(6)H(3)-3-SiMe(3)-2-SH))]- (1b) and [Ni(II)(Cl)(P (o-C(6)H(3)-3-SiMe(3)-2-S)(2)(o-C(6)H(3)-3-SiMe(3)-2-SH))]- (3b) with intramolecular [Ni...H-S] interaction exhibit lower nu(S-H) stretching frequencies (2137 and 2235 cm(-1) for 1b and 3b vs 2250 and 2287 cm(-1) for 1a and 3a, respectively) and smaller torsion angles (27.2 degrees for 3b vs 58.9 and 59.1 degrees for 1a and 3a, respectively). The pendant thiol interaction modes of 1a, 3a, and 3b in the solid state are controlled by the solvent pairs of crystallization. Oxygen oxidation of dinuclear Ni(II)(P(o-C(6)H(3)-3-SiMe(3)-2-S)(2)(o-C(6)H(3)-3-SiMe(3)-2-SH)) (4) yielded thermally stable dinuclear Ni(III)(P(o-C(6)H(3)-3-SiMe(3)-2-S)(2)(o-C(6)H(3)-3-SiMe(3)-2-mu-S)) (5). The two paramagnetic d(7) Ni(III) cores (S = 1/2) with antiferromagnetic coupling (J = -3.13 cm(-1)) rationalize the diamagnetic property of 5. The fully delocalized mixed-valence [Ni(II)-Ni(III)] complexes [Ni2(P(o-C(6)H(3)-3-SiMe(3)-2-S)(3))(2)]- (6) and [Ni(2)(P(o-C(6)H(3)-3-SiMe(3)-2-S)(3))(P(o-C(6)H(3)-3-SiMe(3)-2-S)(2)(o-C(6)H(3)-3-SiMe(3)-2-SCH(3)))] (7) were isolated upon the reduction of 5 and the methylation of 6, respectively. The electronic perturbation from the sulfur methylation of 6 triggers the stronger Ni...Ni interaction and the geometrical rearrangement from the diamond shape of the [NiS(2)Ni] core to the butterfly structure of [Ni(mu-S)(2)Ni] to yield 7 with Ni...Ni distances of 2.6088(1) A. The distinctly different Ni...Ni distances (2.6026(7) for 5 and 2.8289(15) A for 6) and the coordination number of the nickels indicate a balance of geometrical requirements for different oxidation levels of [PS(3)Ni-NiPS(3)] cores of 5 and 6.

摘要

与具有分子内[Ni...H - S]和[Ni - S...H - S]相互作用的[Ni(II)(SePh)(P(o - C₆H₃ - 3 - SiMe₃ - 2 - S)(2)(o - C₆H₃ - 3 - SiMe₃ - 2 - SH))]⁻ (1a)和[Ni(II)(Cl)(P(o - C₆H₃ - 3 - SiMe₃ - 2 - S)(2)(o - C₆H₃ - 3 - SiMe₃ - 2 - SH))]⁻ (3a)相比，具有分子内[Ni...H - S]相互作用的配合物[NiII(SePh)(P(o - C₆H₃ - 3 - SiMe₃ - 2 - S)(2)(o - C₆H₃ - 3 - SiMe₃ - 2 - SH))]⁻ (1b)和[Ni(II)(Cl)(P (o - C₆H₃ - 3 - SiMe₃ - 2 - S)(2)(o - C₆H₃ - 3 - SiMe₃ - 2 - SH))]⁻ (3b)表现出更低的ν(S - H)伸缩频率(1b和3b分别为2137和2235 cm⁻¹，而1a和3a分别为2250和2287 cm⁻¹)以及更小的扭转角(3b为27.2°，而1a和3a分别为58.9°和59.1°)。固态下1a、3a和3b的侧链硫醇相互作用模式受结晶溶剂对的控制。双核[Ni(II)(P(o - C₆H₃ - 3 - SiMe₃ - 2 - S)(2)(o - C₆H₃ - 3 - SiMe₃ - 2 - SH))]₂ (4)的氧氧化产生了热稳定的双核[Ni(III)(P(o - C₆H₃ - 3 - SiMe₃ - 2 - S)(2)(o - C₆H₃ - 3 - SiMe₃ - 2 - μ - S))]₂ (5)。两个具有反铁磁耦合(J = -3.13 cm⁻¹)的顺磁性d⁷ Ni(III)核(S = 1/2)解释了5的抗磁性。完全离域的混合价[Ni(II) - Ni(III)]配合物[Ni₂(P(o - C₆H₃ - 3 - SiMe₃ - 2 - S)(3))(2)]⁻ (6)和[Ni₂(P(o - C₆H₃ - 3 - SiMe₃ - 2 - S)(3))(P(o - C₆H₃ - 3 - SiMe₃ - 2 - S)(2)(o - C₆H₃ - 3 - SiMe₃ - 2 - SCH₃))] (7)分别在5的还原和6的甲基化后被分离出来。6的硫甲基化引起的电子扰动引发了更强的Ni...Ni相互作用以及从[NiS₂Ni]核的菱形到[Ni(μ - S)₂Ni]的蝴蝶结构的几何重排，从而产生7，其Ni...Ni距离为2.6088(1) Å。5和6的明显不同的Ni...Ni距离(5为2.6026(7) Å，6为2.8289(15) Å)以及镍的配位数表明了5和6中[PS₃Ni - NiPS₃]核不同氧化态的几何要求之间的平衡。