Synthesis and reactivity of rhenium carbonyl thiolate complexes, Et4N[Re2(μ-SR)3(CO)6]
作者:P.M. Treichel、M.H. Tegen
DOI:10.1016/0022-328x(88)87088-8
日期:1988.12
Compounds of the formula Et4N[Re2(μ-SR)3(CO)6], (R Me, But, Ph, C6F5) may be prepared in good yields from reactions between various halocarbonylrhenate anions and either the thiolate anion or (n-Bu)3SnSR. These stable, white or off-white, Crystalline species undergo reactions with [Me3O]BF4 in the presence of phosphines to form cis-Re2(μ-SR)2(CO)6(L)2 (L PMe3, PPh3, 12 dppm). When heated in benzene
式Et 4 N [Re 2(μ-SR)3(CO)6 ],(RMe,Bu t,Ph,C 6 F 5)的化合物可以由各种卤代羰基金属酸根阴离子与硫醇根阴离子或(n-Bu)3 SnSR。这些稳定的白色或类白色结晶物质在膦存在下与[Me 3 O] BF 4反应,形成顺式-Re 2(μ-SR)2(CO)6(L)2(LPMe 3,PPH 3,12 dppm)。当在苯中加热时,这些化合物会转化为反式异构体。相反,当它们在四氢呋喃中加热时,一氧化碳会流失,并且会分离出Re 2(μ-SR)2(μ-CO)(CO)4(L)2物质。
Ligand Exchange in Tungsten−Rhenium Acetylide Complexes (C<sub>5</sub>Me<sub>5</sub>)WRe(μ-X)(CCPh)(CO)<sub>5</sub>, X = Br, I, SPh, and O<sub>2</sub>CMe, and the Conversion to Complexes LWRe(μ-SO<sub>2</sub>Ph)(CCPh)(CO)<sub>5</sub>, L = Cp and C<sub>5</sub>Me<sub>5</sub>, Bearing a Sulfinate Bridge via Oxidation Using Hydrogen Peroxide
作者:Chih-Wei Pin、Jiun-Jang Peng、Chin-Wei Shiu、Yun Chi、Shie-Ming Peng、Gene-Hsiang Lee
DOI:10.1021/om9707174
日期:1998.2.1
(C5Me5)WRe(μ-X)(CCPh)(CO)5, X = I and Br (1a,b), were obtained in high yields from the combination of (C5Me5)W(CO)3(CCPh) and Re(CO)5X, X = Br and I. These complexes possess a nearly symmetrical halide bridge and an acetylide ligand, linked to the W atom via σ-bonding and to the Re atom via a π-interaction. The conversion to the corresponding thiolate and acetate complexes LWRe(μ-X)(CCPh)(CO)5 [L = C5Me5
从(C 5 Me 5)W的组合中以高收率获得异双金属乙炔化合物(C 5 Me 5)WRe(μ-X)(CCPh)(CO)5,X = I和Br(1a,b)(CO)3(CCPh)和Re(CO)5 X,X = Br和I。这些络合物具有几乎对称的卤化物桥和乙炔配体,它们通过σ键与W原子相连,并通过a与Re原子相连。 π相互作用。转化为相应的硫醇盐和乙酸盐配合物LWRe(μ-X)(CCPh)(CO)5 [L = C 5 Me 5,X = SPh(2a)和O 2 CMe(3); X = SPh,L = Cp(2b)]是通过在三乙胺或吡啶存在下使卤化物配合物与苯硫酚或与乙酸反应而实现的。(C的相关反应5我5)W(CO)3(CCPh)与[的Re(CO)4(μ-SPH)] 2或[的Re(CO)4(μ-O 2 CME)] 2,得到通过涉及这些二聚起始原料的离解的反应序列形成相同的硫醇盐和乙酸盐复合物。的反应1 -
Tetra-Rhenium Molecular Rectangles as Organizational Motifs for the Investigation of Ligand-Centered Mixed Valency: Three Examples of Full Delocalization
作者:Peter H. Dinolfo、Joseph T. Hupp
DOI:10.1021/ja045457d
日期:2004.12.1
Molecular rectangles having the form ([Re(CO)3]2(X)2)(2)-mu,mu'-(LL)2, where X is either a bridging alkoxide or phenylthiolate group and LL is 4,4'-bipyridine or pyrazine, are characterized by cofacial LL pairs that are in van der Waals contact across the "long" side of the rectangle. Cyclic voltammetry shows that the redox-accessible bridging ligands, LL, are reduced in sequential, one-electron reactions
具有 ([Re(CO)3]2(X)2)(2)-mu,mu'-(LL)2 形式的分子矩形,其中 X 是桥连醇盐或苯硫醇盐基团,LL 是 4,4' -联吡啶或吡嗪的特征是共面 LL 对在矩形的“长”边上呈范德华接触。循环伏安法显示氧化还原可接近的桥接配体 LL 在连续的单电子反应中被还原。单减少的矩形代表一种不寻常的混合价化合物,其中 LL 配体本身是氧化还原中心。这些矩形的混合价形式的光谱电化学测量揭示了近红外区域中强烈的不对称吸收带,指定为间隔跃迁。电吸收(斯塔克光谱)测量显示偶极矩的微小变化,因此在间隔激发时缺乏显着的电荷转移。因此,矩形是 III 类(完全价离域)分子混合价物种的不寻常例子,它们采用直接供体轨道/受体轨道重叠而不是共价键介导的超交换来实现离域所需的大电子耦合强度。
Synthesis and Characterization of Molecular Rectangles Based upon Rhenium Thiolate Dimers
作者:Kurt D. Benkstein、Joseph T. Hupp、Charlotte L. Stern
DOI:10.1021/ic980513v
日期:1998.10.1
Tetrametallic molecular rectangles have been synthesized by combining rhenium(I) thiolate dimers with difunctional pyridyl and pyrazyl type ligands. The proposed rectangular structures are supported by H-1 NMR, MS, and IR absorption measurements. In addition, crystal structures of two of the rectangles are presented showing frameworks with dimensions 3.81 x 11.57 and 3.69 x 7.22 Angstrom, as defined by the rhenium atoms.