Copper(I) and Silver(I) Complexes Supported by the Tridentate [{Ti(η5‑C5Me5)(μ-NH)}3(μ3‑N)] Metalloligand

Copper­(I) and silver­(I) ionic compounds [(L)­M­{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]­[O3SCF3] containing [MTi3N4] cube-type cations have been prepared by reaction of [(CF3SO2O)­M­{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (M = Cu (2), Ag (3)) with a variety of donor molecules L. Treatment of complexes 2 and 3 with NH3 in toluene at room temperature gives the ammonia adducts [(H3N)­M­{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]­[O3SCF3] (M = Cu (4), Ag (5)), whose X-ray crystal structures reveal two cube-type cations associated through hydrogen bonding interactions between the ammine ligands and one oxygen atom of each trifluoromethanesulfonate anion. Analogous treatment of 2 and 3 with 1 equiv of pyridine, 2,6-dimethylphenylisocyanide, tert-butylisocyanide, or triphenylphosphane gives the ionic compounds [(L)­M­{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]­[O3SCF3] (L = py, M = Cu (6), Ag (7); L = CNAr, M = Cu (8), Ag (9); L = CNtBu, M = Cu (10), Ag (11); L = PPh3, M = Cu (12), Ag (13)). The reactions of 2 and 3 with methylenebis­(diphenylphosphane) (dppm) in a 1:1 ratio lead to the single-cube complexes [(dppm)­M­{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]­[O3SCF3] (M = Cu (14), Ag (15)), whereas in a 2:1 ratio give the bisphosphane-bridged double-cube compounds [{M­(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}2(μ-dppm)]­[O3SCF3]2 (M = Cu (16), Ag (17)). Similarly, treatment of 2 or 3 with a half equivalent of ethane-1,2-diylbis­(diphenylphosphane) (dppe) affords double-cube derivatives [{M­(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}2(μ-dppe)]­[O3SCF3]2 (M = Cu (18), Ag (19)). The X-ray crystal structures of 4, 5, 10, 14, 15, and 18 have been determined.

一价铜（Copper(I)）与一价银（Silver(I)）的离子化合物[(L)­M­{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]­[O3SCF3]含有[MTi3N4]立方型阳离子，可通过[(CF3SO2O)­M­{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]（M = Cu (2), Ag (3)）与多种配体分子L的反应制备。将配合物2与3在甲苯中于室温下与氨（NH3）反应，得到氨加合物[(H3N)­M­{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]­[O3SCF3]（M = Cu (4), Ag (5)），其X射线晶体（X-ray crystal）结构显示，两个立方型阳离子通过氨配体与每个三氟甲磺酸根阴离子（trifluoromethanesulfonate anion）的一个氧原子之间的氢键相互作用缔合。采用类似方法，使配合物2与3分别与1当量的吡啶（pyridine）、2,6-二甲基苯基异氰、叔丁基异氰或三苯基膦（triphenylphosphane）反应，得到离子化合物[(L)­M­{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]­[O3SCF3]（L = py, M = Cu (6), Ag (7); L = CNAr, M = Cu (8), Ag (9); L = CNtBu, M = Cu (10), Ag (11); L = PPh3, M = Cu (12), Ag (13)）。当配合物2与3以1:1的摩尔比与亚甲基双(二苯基膦)（methylenebis(diphenylphosphane)，dppm）反应时，生成单立方配合物[(dppm)­M­{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]­[O3SCF3]（M = Cu (14), Ag (15)）；而以2:1的摩尔比反应时，则得到双膦桥联双立方化合物[{M­(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}2(μ-dppm)]­[O3SCF3]2（M = Cu (16), Ag (17)）。类似地，将配合物2或3与半当量的1,2-亚乙基双(二苯基膦)（ethane-1,2-diylbis(diphenylphosphane)，dppe）反应，可得到双立方衍生物[{M­(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}2(μ-dppe)]­[O3SCF3]2（M = Cu (18), Ag (19)）。已测定配合物4、5、10、14、15与18的X射线晶体结构。