Synthesis, Characterization and Potential Electrochemical Properties of Novel Mn-Re Dinuclear Complexes Containing N-Heterocyclic Carbene-carbon Disulfide Ligands†

doi:10.7503/cjcu20130364

Abstract

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

CLC Number:

O621.3⁺91

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2014, 35(1): 68.

Figures/Tables 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

References 33

[1]	Kuninobu Y., Matsuki T., Takai K., J. Am. Chem. Soc., 2009, 131, 9914—9915
[2]	Koumura K., Satoh K., Kamigaito M., J. Polym. Sci. Part A: Polym. Chem., 2009, 47, 1343—1353
[3]	Friestad G. K., Qin J., J. Am. Chem. Soc., 2001, 123, 9922—9923
[4]	Mikata Y., Takahashi K., Noguchi Y., Storr T.,Eur. J. Inorg. Chem., 2012, 217—225
[5]	Perera T., Adhayawardhana P., Fronczek F.R., Marziui P. A., Marzilli L. G., Eur. J. Inorg. Chem., 2012, 618—627
[6]	Galindo A., Miguel D., Pérez J., Coord. Chem. Rev., 1999, 193, 643—690
[7]	Alvarez B., Miguel D., Riera V., Miguel J. A., García-Granda S., Organometallics, 1991, 10, 384—387
[8]	Miguel D., Riera V., Miguel J. A., Gómez M., Soláns X., Organometallics, 1991, 10, 1683—1692
[9]	Li J., Miguel D., Morales M. D., Riera V., Organometallics, 1998, 17, 3448—3453
[10]	Miguel D., Li J., Morales D., Riera V., García-Granda S., Organometallics, 2001, 20, 3063—3069
[11]	Li J., Miguel D., Morales D., Riera V., Aguirre-Pérez A., García-Granda S.,Dalton Trans., 2003, 3264—3269
[12]	Ma Y. Q., Yu L., Hu C. S., Chen X., Li J., Wang H. G., Miguel D., J. Mol. Struct., 2003, 650, 45—48
[13]	Ma Y.Q., Yin N., Li J., Xie Q. L., Miguel D., J.Organomet. Chem.,2004, 689,1949—1955
[14]	Herrmann W. A., Angew. Chem. Int. Ed., 2002, 41, 1290—1309
[15]	Canac Y., Soleilhavoup M., Conejero S., Bertrand G., J. Organomet. Chem., 2004, 689, 3857—3865
[16]	Peris E., Crabtree R. H., Coord. Chem. Rev., 2004, 248, 2239—2246
[17]	Glorius F., Topics in Organometallic Chemistry, Vol. 21, Springer, Berlin, 2007, Ⅻ, 231
[18]	Herrmann W. A., Schütz J., Frey G. D., Herdtweck E., Organometallics, 2006, 25, 2437—2448
[19]	Jacobsen H., Correa A., Costabile C., Cavallo L., J. Organomet. Chem., 2006, 691, 4350—4358
[20]	Mercs L., Labat G., Neels A., Ehlers A., Albrecht M., Organometallics, 2006, 25, 5648—5656
[21]	Viciano M., Mas-Marzá E., Sanau M., Peris E., Organometallics, 2006, 25, 3063—3069
[22]	Capon J.F., Hassnaoui S. E., Gloaguen F., Schollhammer P., Talarmin J., Organometallics, 2005, 24,2020—2022
[23]	Tye J. W., Lee J., Wang H. W., Mejia-Rodriguez R., Reibenspies J. H., Hall M. B., Darensbourg M. Y., Inorg. Chem., 2005, 44, 5550—5552
[24]	Peris E., Crabtree R. H., Coord. Chem. Rev., 2004, 248, 2239—2246
[25]	Naeem S., Thompson A. L., Delaude L., Wilton-Ely J. D. E. T., Chem. Eur. J., 2010, 16, 10971—10974
[26]	Hans M., Willem Q., Wouters J., Demonceau A., Delaude L., Organometallics, 2011, 30, 6133—6142
[27]	Hans M., Wouters J., Demonceau A., Delaude L.,Eur. J. Org. Chem., 2011, 7083—7091
[28]	Alvarez B., García-Granda S., Jeannin Y., Miguel D., Miguel J. A., Riera V., Organometallics, 1991, 10, 3005—3007
[29]	Izutsu K., Acid-Base Dissociation Constants in Dipolar Aprotic Solvents, Blackwell Scientific Publications,Oxford, 1990
[30]	Gloaguen F., Lawrence J. D., Rauchfuss T. B., J. Am. Chem. Soc., 2001, 123, 9476—9477
[31]	Borg S. J., Behrsing T., Best S. P., Razavet M., Liu X., Pickett C. J., J. Am. Chem. Soc., 2004, 126, 16988—16999
[32]	Song L.C., Yang Z. Y., Hua Y. J., Wang H. T., Liu Y., Hu Q. M., Organometallics,2007, 26,2106—2110
[33]	Song L. C., Gao W., Feng C. P., Wang D. F., Hu Q. M., Organometallics, 2009, 28, 6121—6130

Related Articles 15

[1]	BAI Yanqun,WANG Cunguo,LI Xue,FAN Wenqi,SONG Penghao,GU Yuanchun,LIU Faqian,LIU Guangye. Preparation and Electrochemical Properties of S@C Composite Material with High Capacity and Ordered Alignment of Channels ^† [J]. Chem. J. Chinese Universities, 2020, 41(6): 1306.
[2]	DENG Anqiang,LUO Yongchun,XIA Yuanhua,PENG Sihui,MA Weiqin,ZHAO Xudong,YANG Yang,HOU Xiaodong. Effect of Annealing Treatment on Structure and Electrochemical Properties of New Mg-free Y_0.7La_0.3Ni_3.25Al_0.1Mn_0.15Hydrogen Storage Alloys ^† [J]. Chem. J. Chinese Universities, 2020, 41(1): 145.
[3]	CHEN Yaoyan,ZHAO Xin,WANG Zhe,DONG Jie,ZHANG Qinghua. Effects of Preparation Conditions on the Morphologies, Structures and Electrochemical Properties of MXene^† [J]. Chem. J. Chinese Universities, 2019, 40(6): 1249.
[4]	ZHAO Lei,LUO Yongchun,DENG Anqiang,JIANG Wanting. Hydrogen Storage and Electrochemical Properties of the Mg-free A₂B₇-type La_1-_xY_xNi_3.25Mn_0.15Al_0.1 Alloys with Superlattice Structure^† [J]. Chem. J. Chinese Universities, 2018, 39(9): 1993.
[5]	HAO Yuanyuan, WU Qi, LI Ji, GE Chao, MA Chaoying, QIAN Yong, SU Zhi, LIU Hongke. Novel Os^Ⅱ-arene Complexes Based on Bipyridyl Derivative Ligands: Synthesis, Crystal Structure, Anticancer Activity and Interaction with DNA/BSA^† [J]. Chem. J. Chinese Universities, 2018, 39(4): 614.
[6]	ZHANG Bo, HE Jun, HUA Zhengshen, WANG Xin, PENG Huifen. Effect of S $O 4 2 -$ Doping on Electrochemical Properties of the Nasicon Li₃Fe₂(PO₄)₃ Cathode^† [J]. Chem. J. Chinese Universities, 2017, 38(1): 108.
[7]	WANG Xue, YANG Lili, WANG Chunzhong, CHEN Gang, WEI Yingjin. Preparation and Characterizations of Zn-doped Li_1.13Ni_0.3-_xMn_0.57Zn_xO₂ Cathode Materials for Lithium Ion Batteries^† [J]. Chem. J. Chinese Universities, 2015, 36(4): 733.
[8]	KUANG Daizhi, FENG Yonglan, YU Jiangxi, ZHANG Fuxing, JIANG Wujiu, PENG Yan, ZHU Xiaoming, TAN Yuxing. Microwave Assisted Solid-state Synthesis, Crystal Structure, Properties of the Coordination Polymer Constructed from Tricyclohexyltin Hydroxide and o-Ferrocenylcarbonyl Benzoic Acid^† [J]. Chem. J. Chinese Universities, 2014, 35(8): 1629.
[9]	SUN Hong-Dan, HE Shi-Ci, XIA Bing-Bo, FANG Guo-Qing, LIU Wei-Wei, QIU Guang-Chao, ZHANG Qian, KANEKO Shingo, ZHENG Jun-Wei, LI De-Cheng. Preparation, Structure and Electrochemical Properties of LiNi_0.5-xAl_2xMn_1.5-xO₄(0≤2x≤0.15) by Spray-Dry Process [J]. Chem. J. Chinese Universities, 2013, 34(5): 1059.
[10]	KE Chuan, CAI Fang-Gong, YANG Feng, CHENG Cui-Hua, ZHAO Yong. Preparation and Photoelectrical Properties of CuS/TiO₂ Nanotube Heterojunction Arrays [J]. Chem. J. Chinese Universities, 2013, 34(2): 423.
[11]	LIU Wei-Wei, KANEKO Shingo, FANG Guo-Qing, SUN Hong-Dan, XIA Bing-Bo, ZHENG Jun-Wei, LI De-Cheng. Structure and Electrochemical Properties of xLi[Li_1/3Mn_2/3] O₂-(1-x)LiNi_5/12Mn_5/12Co_2/12O₂(0≤x≤0.8) [J]. Chem. J. Chinese Universities, 2013, 34(10): 2395.
[12]	WANG Huan-Feng, GAO Yan-Ying, JIANG Qian-Qian, MA Cong, WANG Xing-Yao. Hydrothermal Synthesis and Electrochemical Characteristics of Cathode Materials Li₃V₂(PO₄)₃/C [J]. Chem. J. Chinese Universities, 2012, 33(10): 2326.
[13]	GAO Zhi-Jie, KANG Long, LUO Yong-Chun. Influence of Magnesium Content on Structure and Performance of A₂B₇-type RE-Mg-Ni Hydrogen Storage Alloys [J]. Chem. J. Chinese Universities, 2012, 33(09): 2035.
[14]	GU Ning-Yu, AO He, PEI Jian-Jun. Preparation and Characterization of Composite Polymer Electrolytes Containing Surface-modified Nano Silica [J]. Chem. J. Chinese Universities, 2012, 33(06): 1295.
[15]	SU Zhi*, XU Mao-Wen, YE Shi-Hai, WANG Yong-Long. Synthesis and Electrochemical Properties of Monoclinic Layered Structure LiMn_0.97Al_0.03O_2-x(PO₄)_x Materials [J]. Chem. J. Chinese Universities, 2010, 31(2): 247.