Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague , Hlavova 2030, 12840 Prague 2, Czech Republic.
Inorg Chem. 2014 Jan 6;53(1):568-77. doi: 10.1021/ic4026848. Epub 2013 Dec 17.
1'-(Diphenylphosphino)-1-cyanoferrocene (3), a new donor-asymmetric ferrocene ligand obtained in two steps from 1'-(diphenylphosphino)ferrocene-1-carboxaldehyde, reacts with CuCl at a Cu/3 molar ratio of 1:1 to give the heterocubane complex [Cu(μ3-Cl)(3-κP)]4 (4). When the Cu/3 ratio is changed to 1:2 or 1:3, the reaction takes a different course, producing the P,N-bridged dimer [CuCl(3-κP)(μ(P,N)-3)]2 (5) after crystallization. Notably, CuBr and CuI behave differently, affording the corresponding 2D coordination polymers [CuX(μ(P,N)-3)]n [X = I (7), and Br (8)], regardless of the Cu/3 ratio. Reaction of 3 with sources of naked Cu(+), such as Cu(MeCN)4 salts or their synthetic equivalents, provides the 1D coordination polymer [Cu(MeCN-κN)(μ(P,N)-3)][BF4] (9) or salts of a quadruply bridged dicopper(I) cation, [Cu2(μ(P,N)-3)4]X2 ([10]X2), depending on the Cu/3 molar ratio (1:1 vs 1:2 and 1:3). Except for 4, in which 3 binds as a simple P-monodentate ligand, the complexes reported here represent the first structurally characterized compounds in which a phosphinonitrile ligand coordinates through both of its soft donor moieties, thereby extending the coordination chemistry of these ligands.
1'-(二苯膦基)-1-氰基二茂铁（3），一种新的给体不对称二茂铁配体，可由 1'-(二苯膦基）二茂铁-1-甲醛两步合成，与 CuCl 在 Cu/3 摩尔比为 1:1 下反应，生成杂核立方烷配合物[Cu(μ3-Cl)(3-κP)]4（4）。当 Cu/3 比例变为 1:2 或 1:3 时，反应会采取不同的途径，结晶后生成 P,N-桥联二聚体[CuCl(3-κP)(μ(P,N)-3)]2（5）。值得注意的是，CuBr 和 CuI 的行为不同，无论 Cu/3 比例如何，都会生成相应的 2D 配位聚合物[CuX(μ(P,N)-3)]n [X = I（7）和 Br（8）]。3 与裸露的 Cu(+)源（如Cu(MeCN)4盐或其合成等价物）反应，提供了 1D 配位聚合物[Cu(MeCN-κN)(μ(P,N)-3)][BF4]（9）或四重桥联二铜（I）阳离子盐[Cu2(μ(P,N)-3)4]X2([10]X2)，这取决于 Cu/3 摩尔比（1:1 对 1:2 和 1:3）。除了 4，其中 3 作为简单的 P-单齿配体结合外，这里报道的配合物代表了第一个通过其两个软给体部分配位的膦腈配体的结构特征化合物，从而扩展了这些配体的配位化学。
