RT info:eu-repo/semantics/article
T1 Cadmium and mercury complexes containing trinuclear titanium imido-nitrido metalloligands
A1 Martín Alonso, Avelino
A1 Mena Montoro, Miguel
A1 Pérez Redondo, Adrián
A1 Yélamos Sánchez, Carlos
K1 Cadmium
K1 Cage compounds
K1 Mercury
K1 Nitrides
K1 Titanium
K1 Química
K1 Chemistry
AB Several heterometallic nitrido complexes have been prepared from the reaction of the trinuclear imido-nitrido titanium complex [{Ti(5-C5Me5)(mu-NH)}3(mu 3-N)] (1) with cadmium and mercury derivatives. Treatment of 1 with cadmium dichloride or cadmium diiodide in toluene afforded the adducts [X2Cd{(mu 3-NH)3Ti3(5-C5Me5)3(mu 3-N)}] [X = Cl (2), I (3)]. Complex 2 reacted with lithium reagents [LiR] in toluene to give the cube-type derivatives [RCd{(mu 3-N)(mu 3-NH)2Ti3(5-C5Me5)3(mu 3-N)}] [R = CH2SiMe3 (4), C=CSiMe3 (5), C5H4(SiMe3) (6), N(SiMe3)2 (7)]. The amido complex 7 reacted with 1 equiv. of 1 to give the corner-shared double-cube complex [Cd{(mu 3-N)(mu 3-NH)2Ti3(5-C5Me5)3(rho 3-N)}2] (8) by means of bis(trimethylsilyl)amine elimination. Treatment of 1 with mercury(II) iodide in toluene gave the adduct [I2Hg{(mu 3-NH)3Ti3(5-C5Me5)3(mu 3-N)}] (9), which reacted with [K{N(SiMe3)2}] to afford [Hg{(mu 3-N)2Ti3(5-C5Me5)3(mu-NH)(mu 3-N)}]2 (10) through the amido mercury intermediate [{(Me3Si)2N}Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}] (11). Compound 11 and the analogous alkyl derivative [(Me3SiCH2)Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}] (12) were characterised by NMR spectroscopy upon the treatment of 1 with [Hg{N(SiMe3)2}R] [R = N(SiMe3)2, CH2SiMe3]. Complex [Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}2] (13), with one bridging mercury atom between two titanium trinuclear systems, was obtained upon treatment of HgI2 with the potassium derivative [K(mu 4-N)(mu 3-NH)2{Ti3(5-C5Me5)3(mu 3-N)}]2. Complexes 3, 5 and 8 were characterised by single-crystal X-ray diffraction analysis.
SN 1434-1948
YR 2011
FD 2011-12
LK http://hdl.handle.net/10017/38514
UL http://hdl.handle.net/10017/38514
LA eng
NO Ministerio de Educación y Ciencia de España
DS MINDS@UW
RD 18-abr-2024