新型含N-杂环卡宾二硫化碳配体的锰铼金属双核化合物的合成、表征及电化学性质

doi:10.7503/cjcu20130364

摘要/Abstract

摘要：

合成了一系列含N-杂环卡宾二硫化碳加合物配体的锰铼金属有机化合物, 其中包括3种单核化合物和3种双核化合物, 对它们的结构进行了表征, 并研究其反应性和电化学性质. 与三烷基膦二硫化碳配体相比, 含N-杂环卡宾二硫化碳加合物配体的锰铼金属有机化合物展现出不同的反应特性. 研究结果表明, [MnRe(CO)₆(μ-H){μ-CH₃SC(S)IMes₂}]配合物具有催化质子还原成氢气的能力.

关键词: N-杂环卡宾二硫化碳加合物, 锰铼双核金属有机化合物, 单核金属有机化合物, 电化学性质

Abstract:

The ⅦB group organometallic compounds of Mn or Re have been widely investigated on the synthesis, characterization, possible reactivity properties and catalytic activities. Compared to the use of NHCs as ligands, the exploration in the field of carbene dithiocarboxylate(NHC·CS₂) coordination with metal is very lack. Herein reported the synthesis, characterization, reactivity and electrochemical studies of a series of Mn and Re organometallic complexes containing NHC·CS₂ ligands, concluding three mononuclear complexes and three dinuclear complexes. Those compounds were characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR. Compared to R₃P·CS₂ ligands, Mn-Re dinuclear organometallic complexes containing NHC·CS₂ ligands showed different reactivity. The electrochemical studies of [MnRe(CO)₆(μ-H){μ-CH₃SC(S)·IMes₂}] were explored, and the results showed it possesses the potential catalytic property for proton reduction of acetic acid to give hydrogen under electrochemical conditions, which may be considered as a model in the research of the active site of [Fe-Fe] hydrogenases.

Key words: NHC·CS2, Mn-Re dinuclear complex, Mononuclear complex, Electrochemical property

中图分类号:

O621.3⁺91

TrendMD:

赵甲, 孙华冰, 柳凌艳, 常卫星, 李靖. 新型含N-杂环卡宾二硫化碳配体的锰铼金属双核化合物的合成、表征及电化学性质. 高等学校化学学报, 2014, 35(1): 68.

ZHAO Jia, SUN Huabing, LIU Lingyan, CHANG Weixing, LI Jing. Synthesis, Characterization and Potential Electrochemical Properties of Novel Mn-Re Dinuclear Complexes Containing N-Heterocyclic Carbene-carbon Disulfide Ligands^†. Chem. J. Chinese Universities, 2014, 35(1): 68.

图/表 8

Scheme 1 Syntheses of [MnRe(CO)6(μ-NHC·CS2)]

Fig.1 Molecular structures of complexes 4(A) and 5(B) with 30% probability level ellipsoids

Table 1 Selected bond lengths(nm) and bond angles(°) for complexex 4, 5 and MnRe(CO)6(μ-S2C·PCy3)

Bond	Complex 4	Complex 5	MnRe(CO)₆(μ-S₂CPCy₃)
Rel—Mnl	0.2805(19)	0.2836(16)	0.2830(1)
Re1—Sl	0.2403(3)	0.2426(2)	0.2407(1)
Rel—S2	0.2401(3)	0.2407(2)	0.2395(1)
Mnl—Sl	0.2344(3)	0.2360(3)	0.2351(2)
Mn1—S2	0.2341(3)	0.2346(3)	0.2343(2)
Mnl—C7	0.2050(9)	0.2022(9)	0.2030(5)
C7—C8	0.1446(13)	0.1463(10)
Sl—C7—S2	106.8(5)	106.8(4)	105.6(3)
S1—Rel—S2	72.1(9)	71.9(8)	71.8(1)
Sl—Mnl—S2	74.2(10)	74.1(10)	73.7(1)

Scheme 2 Syntheses of [MnRe(CO)6(μ-H){μ-CH3SC(S)IMes2}]

Fig.2 Molecular structure of complex 7 with 30% probability level ellipsoids

Table 2 Selected bond lengths(nm) and bond angles(°) for complex 7

Re1—Mn1	0.2951(10)	Mn1—S1	0.2258(18)
Mn1—C8	0.2126(6)	Re1—S1	0.2445(16)
Re1—S2	0.2485(16)	C8—C9	0.1471(8)
Mn1—S1—Re1	77.6(5)	S2—C8—Mn1	112.2(3)
S1—C8—S2	103.7(3)

Table 3 Crystal data and structure refinement parameters for complexes 4, 5 and 7

Complex	4(r90304c)	5(r90324c)	7 (r90504a)
Empirical formula	C₂₈H₂₄MnN₂O₆ReS₂	C₁₇H₁₀MnN₂O₆ReS₂	C₂₉H₂₈MnN₂O₆ReS₂
Formula weight	789.75	643.53	805.79
Temperature/K	113(2)	293(2)	113(2)
Wavelength/nm	0.071073	0.071073	0.071073
Crystal system	Triclinic	Triclinic	Monoclinic
Space group	P $1 ˉ$	P $1 ˉ$	P2(1)/c
a/nm	0.8497(17)	1.0830(2)	1.1102(2)
b/nm	1.0365(2)	1.3291(3)	1.7812(4)
c/nm	1.9047(4)	1.4610(3)	1.7391(4)
α/(°)	74.22(3)	88.98(3)	90
β/(°)	88.19(3)	81.60(3)	103.41(3)
γ/(°)	78.09(3)	83.12(3)	90
V/nm³	1.5790(5)	2.0655(7)	3.3453(12)
Z	2	4	4
Calcd. density/(Mg·m^-3)	1.661	2.069	1.600
Abs. coeff/mm^-1	4.402	6.704	4.157
F(000)	772	1224	1584
Crystal size	0.20 mm×0.18 mm×0.14 mm	0.20 mm×0.14 mm×0.10 mm	0.20 mm×0.18 mm×0.12 mm
θ range/(°)	2.45—25.02	2.54—25.02	1.89—25.02
No. of reflections collected	11308	15101	24983
No. of unique data, R_int	5512, 0.0786	7238, 0.0552	5902, 0.0549
Transmission(max and min)	0.5777—0.4730	0.5537—0.3474	0.6353—0.4902
No. of data/restraints/parameters	5512/66/367	7238/12/513	5902/0/381
GOF on F²	1.063	0.932	1.097
Final R indices[I>2σ(I)]	R₁=0.0561, wR₂=0.1603	R₁=0.0481, wR₂=0.1031	R₁=0.0392, wR₂=0.0904
R indices(all data)	R₁=0.0665, wR₂=0.1732	R₁=0.0692, wR₂=0.1109	R₁=0.0459, wR₂= 0.0931
Largest diff. peak, hole/(e·nm^-3)	1995, -2570	1402, -2261	1780, -1223

Table 3 Crystal data and structure refinement parameters for complexes 4, 5 and 7

Complex	4(r90304c)	5(r90324c)	7 (r90504a)
Empirical formula	C₂₈H₂₄MnN₂O₆ReS₂	C₁₇H₁₀MnN₂O₆ReS₂	C₂₉H₂₈MnN₂O₆ReS₂
Formula weight	789.75	643.53	805.79
Temperature/K	113(2)	293(2)	113(2)
Wavelength/nm	0.071073	0.071073	0.071073
Crystal system	Triclinic	Triclinic	Monoclinic
Space group	P $1 ˉ$	P $1 ˉ$	P2(1)/c
a/nm	0.8497(17)	1.0830(2)	1.1102(2)
b/nm	1.0365(2)	1.3291(3)	1.7812(4)
c/nm	1.9047(4)	1.4610(3)	1.7391(4)
α/(°)	74.22(3)	88.98(3)	90
β/(°)	88.19(3)	81.60(3)	103.41(3)
γ/(°)	78.09(3)	83.12(3)	90
V/nm³	1.5790(5)	2.0655(7)	3.3453(12)
Z	2	4	4
Calcd. density/(Mg·m^-3)	1.661	2.069	1.600
Abs. coeff/mm^-1	4.402	6.704	4.157
F(000)	772	1224	1584
Crystal size	0.20 mm×0.18 mm×0.14 mm	0.20 mm×0.14 mm×0.10 mm	0.20 mm×0.18 mm×0.12 mm
θ range/(°)	2.45—25.02	2.54—25.02	1.89—25.02
No. of reflections collected	11308	15101	24983
No. of unique data, R_int	5512, 0.0786	7238, 0.0552	5902, 0.0549
Transmission(max and min)	0.5777—0.4730	0.5537—0.3474	0.6353—0.4902
No. of data/restraints/parameters	5512/66/367	7238/12/513	5902/0/381
GOF on F²	1.063	0.932	1.097
Final R indices[I>2σ(I)]	R₁=0.0561, wR₂=0.1603	R₁=0.0481, wR₂=0.1031	R₁=0.0392, wR₂=0.0904
R indices(all data)	R₁=0.0665, wR₂=0.1732	R₁=0.0692, wR₂=0.1109	R₁=0.0459, wR₂= 0.0931
Largest diff. peak, hole/(e·nm^-3)	1995, -2570	1402, -2261	1780, -1223

Fig.3 Cyclic voltammograms of complexes 4(A) and 7(B)(1.0 mmol/L) in 0.1 mol/L n-Bu4NPF6/MeCN at a scan rate of 100 mV/s

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