Ligandverhalten von P-funktionellen Organozinnhalogeniden: Nickel(II)-, Palladium(II)- und Platin(II)-halogenid-Komplexe mit Me2(Cl)SnCH2CH2PPh2

Abstract

Inhaltsu È bersicht. Me 2 (Cl)SnCH 2 CH 2 PPh 2 (1) reagiert mit Nickel(II)-, Palladium(II)-und Platin(II)-halogeniden im Molverha È ltnis 2 : 1 zu den Komplexen [MX 2 {PPh 2 -CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (M = Ni, Pd, Pt; X = Cl, Br) (3±6, 9, 10) (7, 8: M = Ni; Br anstelle von Cl). Von den Nickelkomplexen wurden jeweils das planare (3, 5, 7) und das tetraedrische (4, 6, 8) Isomer isoliert und charakterisiert. In Lo È sung liegen beide Isomere im Gleichgewicht vor. Die Kristallstrukturen und NMR-Daten belegen fu È r die planaren Nikkelkomplexe 3, 5, 7 sowie [MCl 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (9: M = Pd; 10: M = Pt) die Existenz von intra-und intermolekularen M±Hal´´´Sn-Bru È cken. Im Ligand : Metall-Verha È ltnis 3 : 1 werden die Komplexe [M Å Cl{PPh 2 CH 2 -CH 2 Sn 7 Cl 2 Me 2 }{PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (11: M = Pd; 12: M = Pt) gebildet, die als Zwitterionen vorliegen. Die Dehalogenierung von [PdCl 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (9) mit Natriumamalgam bzw. Graphitkalium (C 8 K) fu È hrt zu den Palladacyclen cis-[Pd{PPh 2 CH 2 CH 2 SnMe 2 } 2 ] (13) und trans-[Pd(Cl)PPh 2 CH 2 CH 2 SnMe 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 }] (14). Von den Verbindungen 1, 3, 9, 11 und 12 wurden die Kristallstrukturen bestimmt. Sa È mtliche Verbindungen sind 1 H-, 31 P-und 119 Sn-NMR-spektroskopisch charakterisiert.Abstract. Me 2 (Cl)SnCH 2 CH 2 PPh 2 (1) reacts with Ni II , Pd II , and Pt II halides in molar ratio 2 : 1 forming the complexes [MX 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (M = Ni, Pd, Pt; X = Cl, Br) (3±6, 9, 10) (7, 8: M = Ni; Br instead of Cl). The nickel complexes were isolated and characterized both as the planar (3, 5, 7) and the tetrahedral (4, 6, 8) isomer. Crystal structure analyses and NMR data indicate for the planar nikkel complexes 3, 5, 7 and [MCl 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (9: M = Pd; 10: M = Pt) the existence of intra and intermolecular M±Hal´´´Sn bridges. In a ligand : metal molar ratio of 3 : 1 the complexes [M Å Cl{PPh 2 CH 2 CH 2 Sn 7 Cl 2 Me 2 }-{PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (11: M = Pd; 12: M = Pt) are formed which represent intramolecular ion pairs. By dehalogenation of [PdCl 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (9) with sodium amalgam and graphite potassium (C 8 K), respectively, the palladacycles cis-[Pd{PPh 2 CH 2 CH 2 SnMe 2 } 2 ] (13) and trans-[Pd(Cl)PPh 2 CH 2 CH 2 SnMe 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 }] (14) are formed. From the compounds 1, 3, 9, 11, and 12 the crystal structures are determined. All compounds are characterized by 1 H, 31 P, and 119 Sn NMR spectroscopy.

Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

“…Disproportionation of RSnX 3 into R 2 SnX 2 and SnX 4 upon reaction with phosphines was also observed in some systems [290,291,302]. Intramolecular coordination of P-functionalised organotin halides produces more stable complexes [305][306][307][308]. For example, chloro(3-(t-butyl(phenyl)phosphino)propyl)dimethyltin is trigonal bipyramidal with apical Cl,P [306] (Fig.…”

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

“…However, it may be worth mentioning that other heteroatoms (e.g., sulfur [127][128][129] and phosphorus [130][131][132]) also form similar interactions. Ether and carbonyl oxygens as well as amine, pyridine, and cyano nitrogens can all be involved in such interactions, and the geometries observed indicate that the lone pair of the heteroatom is directed towards the germanium/tin atom independent of the hybridization of the oxygen/nitrogen atom (which can be sp 3 , sp 2 , or sp).…”

Organometallic Polymers of Germanium, Tin and Lead

“…The Sn−P distance in 169 amounts to 3.065(1)Å, which is comparable to the Sn−P distance of 3.078(2)Å in the monomeric, intramolecularly coordinated Me 2 ClSnCH 2 CH 2 CH 2 PPhBu-t 411 . The bromo-substituted analogue of 169, Me 2 BrSnCH 2 CH 2 PPh 2 , was also suggested to adopt a polymeric chain structure similar to that established for 169 238 . …”

“…An intermolecular P−Sn coordination was previously suggested to occur in Me 2 ClSnCH 2 CH 2 PPh 2 (169) 409,410 which was based on NMR and 119 Sn Mössbauer spectroscopic data. Recently, X-ray crystal structure analyses confirmed the previous assumption and showed a linear polymer with pentacoordinated tin atoms 238 . The phosphorus and the chlorine atoms are located in axial positions.…”