Heterocubane Phosphoraniminato Complexes of Cadmium

Abstract

Phosphoraniminato complexes of cadmium [CdX(NPEt 3 )] 4 {X ) Cl (1), Br (2), I (3), [CdI(NPMe 3 )] 4 (4)} are formed by the reaction of cadmium dihalides with silylated phosphoranimines Me 3 SiNPR 3 (R ) Me, Et) in the presence of a fluoride source, e.g. NaF, at elevated temperatures. High yields can be achieved when R ) Et and X is a heavy halogen. The exocyclic bromo function in complex 2 can be replaced by reaction with organolithium reagents to give organocadmium compounds [CdMe(NPEt 3 )] 4 (5) and [Cd(C 2 SiMe 3 )(NPEt 3 )] 4 (6) in excellent yields. Complexes 1-6 consist of a [Cd 4 N 4 ] heterocubane core in which the cadmium atoms are linked by µ 3 -N bridges of the phosphoraniminato ligand with the cubane angles being close to 90°. The crystal structure of an unsymmetrical cubane [Cd 4 I 4 (OSiMe 3 )(NPEt 3 ) 3 ] (7) is reported, in which one of the phosphoraniminato moieties has been replaced by a silyloxy function. All complexes are colorless oxygen-and moisture-sensitive crystalline materials, the heterocubane structure of which has been shown by crystal structure determinations and is consistent with spectroscopic findings, including IR, NMR, and mass spectra.

Cadmium and Mercury Complexes Containing Trinuclear Titanium Imido‐Nitrido Metalloligands

“…2.134(5) Å]. [21] The alkynyl ligand is linear with a Cd(1)-C(41)-C(42) angle of 179.5(4)°and a C(41)ϵC(42) bond length of 1.208(5) Å, all of which are typical for these ligands. [17] Within the organometallic ligand, the average bond lengths and angles are similar to those determined in the uncoordinated ligand 1.…”

Phosphoraneiminato Complexes of Manganese and Cobalt with Heterocubane Structure

“…The only lately known phosphoraneiminato complexes of divalent transition metals of the [MX(NPR 3 )] 4 -type with heterocubane structure, [1] of which representatives with M = Mn, [2±5] Fe, [6] Co, [7,8] Ni, [4,9,10] Zn, [7, 11±14], and Cd [11,15] are described, are of special interest for structural reasons and because of their bonding conditions [1]. The complexes with X = Cl, Br, and I gained preparative and partly catalytic significance also because of the substitutability of the terminally bonded halogen atoms for triflate, hydride, alkyl, alkenyl, and alkynyl residues, [1].…”

Cobalt(II)-organische Phosphaniminato-Komplexe mit Heterocuban-Struktur. Kristallstrukturen von [CoBr(NPR3)]4 mit R = Me, Et, [Co(C≡C-CMe3)(NPMe3)]4 und [Co(C≡C-SiMe3)(NPEt3)]4

“…Phosphaniminato-Komplexe zweiwertiger Ûbergangsmetalle vom Typ [MX(NPR 3 )] 4 mit M 4 N 4 -Heterocuban-Struktur sind von den Elementen Mangan [1,2], Eisen [3], Cobalt [1,4], Nickel [2,5], Zink [4,6] und Cadmium [7] mit X = Cl, Br und I sowie mit R = Me und Et wohlbekannt und strukturell eingehend untersucht. Versuche, die terminal gebundenen Halogen-Liganden durch organische Reste mit Metall±C±r-Bindung unter Erhalt der Heterocuban-Geru È ste herzustellen, waren bisher nur bei Mangan mit d 5 - [8,9] und bei Zink [10,11] und Cadmium [10,7] mit d 10 -Elektronenkonfiguration erfolgreich.…”

“…Versuche, die terminal gebundenen Halogen-Liganden durch organische Reste mit Metall±C±r-Bindung unter Erhalt der Heterocuban-Geru È ste herzustellen, waren bisher nur bei Mangan mit d 5 - [8,9] und bei Zink [10,11] und Cadmium [10,7] mit d 10 -Elektronenkonfiguration erfolgreich. Wir berichten hier u È ber die ersten Beispiele cobaltorganischer Komplexe dieses Typs mit d 7 -Elektronenkonfiguration.…”