Silver(i) complexes with 1'-(diphenylphosphino)-1-cyanoferrocene: the art of improvisation in coordination.
Silver(i) complexes with 1'-(diphenylphosphino)-1-cyanoferrocene: the art of improvisation in coordination.
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银(i)与1-(二苯基膦)-1-氰基二茂铁的配合物：即兴协调的艺术。
DOI：
10.1039/c6dt01843b
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发表时间：
2016
影响因子：
4
通讯作者：
P. Štěpnička
中科院分区：
文献类型：
--
作者：
Karel Škoch;F. Uhlík;I. Císařová;P. Štěpnička
1′-（二苯基膦）-1-氰二茂（）与卤化银(i)以1:1的金属配体比反应生成杂环烷配合物[Ag(μ3-X)(-κ p)]4，其中X = Cl (), Br (), i（）。此外，AgCl与2等的反应生成氯桥二聚体[(μ- cl)2{Ag(-κP)2}2]()，也可能生成[(μ(P，N)-){AgCl(-κP)}]2（）。与AgCN的类似反应只产生不溶性配位聚合物[(-κ p)2Ag(NC)Ag(CN)]n()，而与AgSCN的类似反应则产生杂己烷[Ag(-κ p)(μ-SCN-S，S, n)]4（）和硫氰酸酯桥接的银(i)配合物[Ag(-κ p)2(μ-SCN-S, n)]2()，从而类似于AgCl-体系中的反应。尝试与AgF反应，产物定义不清，其中鉴定出[Ag(-κP)2(μ-HF2)]2（）和[(μ-SiF6){Ag(-κP)2}2]（）。后一种化合物也是由Ag2[SiF6]和。与AgClO4或Ag[BF4]之间的反应产生[(μ(P，N)-)Ag(ClO4-κ o)]2（）和[(μ(P，N)-)Ag(BF4-κ f)]2（）的银络合物，其中心呈伪线性，与反阴离子弱配位。与Ag[SbF6]进行类似的反应，然后由乙酸乙酯结晶，得到类似的配合物，尽管是配位溶剂，[(μ(P，N)-)Ag(AcOEt-κ o)]2[SbF6]2（）。最终，在Ag(i)中心无任何附加配体的化合物[(μ(P，N)-)Ag]2[B(C6H3(CF3)2-3,5)4]2()，与银(i)四烷基[3,5-双（三氟甲基）苯基]硼酸盐反应得到。Ag[BF4]与两种等量物反应生成独特的配位聚合物[Ag(-κP)(μ(P，N)-)] N [BF4] N()，其结构包含一个磷二茂配体作为P，N螯合物，另一个与相邻的Ag(i)中心形成桥接。所有这些化合物都通过单晶x射线晶体学进行了结构表征，揭示了银与其阴离子配体之间的键的长度通常超过各自共价半径的总和，这与密度泛函理论（DFT）水平的理论计算结果一致。表明银与磷之间形成标准的共价键（软酸/软碱相互作用），而银与配体的腈基（如果配位）或支撑阴离子之间的相互作用主要是静电性质的。
1'-(Diphenylphosphino)-1-cyanoferrocene () reacts with silver(i) halides at a 1 : 1 metal-to-ligand ratio to afford the heterocubane complexes [Ag(μ3-X)(-κP)]4, where X = Cl (), Br (), and I (). In addition, the reaction with AgCl with 2 equiv. of leads to chloride-bridged dimer [(μ-Cl)2{Ag(-κP)2}2] () and, presumably, also to [(μ(P,N)-){AgCl(-κP)}]2 (). While similar reactions with AgCN furnished only the insoluble coordination polymer [(-κP)2Ag(NC)Ag(CN)]n (), those with AgSCN afforded the heterocubane [Ag(-κP)(μ-SCN-S,S,N)]4 () and the thiocyanato-bridged disilver(i) complex [Ag(-κP)2(μ-SCN-S,N)]2 (), thereby resembling reactions in the AgCl- system. Attempted reactions with AgF led to ill-defined products, among which [Ag(-κP)2(μ-HF2)]2 () and [(μ-SiF6){Ag(-κP)2}2] () could be identified. The latter compound was prepared also from Ag2[SiF6] and . Reactions between and AgClO4 or Ag[BF4] afforded disilver complexes [(μ(P,N)-)Ag(ClO4-κO)]2 () and [(μ(P,N)-)Ag(BF4-κF)]2 () featuring pseudolinear Ag(i) centers that are weakly coordinated by the counter anions. A similar reaction with Ag[SbF6] followed by crystallization from ethyl acetate produced an analogous complex, albeit with coordinated solvent, [(μ(P,N)-)Ag(AcOEt-κO)]2[SbF6]2 (). Ultimately, a compound devoid of any additional ligands at the Ag(i) centers, [(μ(P,N)-)Ag]2[B(C6H3(CF3)2-3,5)4]2 (), was obtained from the reaction of with silver(i) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The reaction of Ag[BF4] with two equivalents of produced unique coordination polymer [Ag(-κP)(μ(P,N)-)]n[BF4]n (), the structure of which contained one of the phosphinoferrocene ligands coordinated as a P,N-chelate and the other forming a bridge to an adjacent Ag(i) center. All of these compounds were structurally characterized by single-crystal X-ray crystallography, revealing that the lengths of the bonds between silver and its anionic ligand(s) typically exceed the sum of the respective covalent radii, which is in line with the results of theoretical calculations at the density-functional theory (DFT) level, suggesting that standard covalent dative bonds are formed between silver and phosphorus (soft acid/soft base interactions) while the interactions between silver and the ligand's nitrile group (if coordinated) or the supporting anion are of predominantly electrostatic nature.
影响因子：
15
作者：
Halper, Sara R.;Do, Loi;Cohen, Seth M.
通讯作者：
Cohen, Seth M.