Coordination chemistry of stannylene-based Lewis pairs – insertion into M–Cl and M–C bonds. From base stabilized stannylenes to bidentate ligands

Abstract

The coordination chemistry of intramolecular stannylene phosphorus Lewis pairs incorporated into four membered ring systems is presented. Previously reported coordination chemistry of stannylene and phosphorus towards palladium(0) is extended by using Pd(nbe) as a precursor, yielding co-ligand free complexes. An equilibrium of one or two stannylene phosphorus ligands coordinated to Pd(0) was observed with tin acting either as a donor or an acceptor towards palladium. Furthermore, the reactions with transition metal(i) chlorides, [(cod)IrCl], [(cod)RhCl] and MeSAuCl are reported. They proceed via insertion of stannylene into the M-Cl bonds, yielding metal complexes with chelating stannide phosphorus ligands. For gold, a dinuclear complex with bridging P-Sn ligands was formed. Furthermore, the reaction of a P → Sn Lewis pair in a three membered ring system with (cod)PtMe is reported.

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me3P)2(Ph3P)Rh≡E‐Ar*] (E=Sn, Pb)

“…Due to coordination of the rhodium atom at a phenyl moiety of the terphenyl substituent in compounds 8 and 9 double sets of 1 H and 13 C NMR signals were found for the trip‐substituents of the terphenyl group. This type of terphenyl‐rhodium coordination is already known in the literature [21] . Both heteroelement NMR signals were found at high frequencies ( 119 Sn NMR 8 , 3112 ppm; 207 Pb NMR 9 , 11 269 ppm) in comparison to known organometallostannylenes or plumbylenes [7, 17, 18, 22] .…”

Flexible and Versatile Pincer-Type PGeP and PSnP Ligand Frameworks

“…[19][20][21][22][23][24] However, so far they are limited to ECE or ENE systems (E = Si, Ge) and only very recently, the first phosphine-functionalized germylene and stannylene ligands and their applications have been reported. [25][26][27][28] Given that polydentate carbene ligands and their polymetallic complexes often feature interesting properties such as photoluminescent behavior, [29][30][31] we were interested in substituting the carbene carbon atom by its heavier analogues and explore the properties of such compounds. Thereby, we used a PNHNHP proligand developed by Thomas and co-workers (pictured in Scheme 1), whose synthesis is straightforward, feasible on a multi-gram scale and has been extensively investigated.…”

Synthese und Hydrierung schwerer Homologe eines Rhodium‐Carbins: [(Me3P)2(Ph3P)Rh≡E‐Ar*] (E=Sn, Pb)

“…Aufgrund der Koordination des Rhodiumatoms an eine Phenyleinheit des Terphenylsubstituenten weisen Verbindung 8 und 9 im 1 H‐ und 13 C‐NMR den doppelten Signalsatz für die Trip‐Substituenten der Terphenylgruppe auf. Diese Art der Therphenyl‐Rhodium‐Koordination ist bereits literaturbekannt [21] …”

“…Aufgrund der Koordination des Rhodiumatoms an eine Phenyleinheit des Te rphenylsubstituenten weisen Verbindung 8 und 9 im 1 H-und 13 C-NMR den doppelten Signalsatz fürd ie Trip-Substituenten der Terphenylgruppe auf.D iese Art der Therphenyl-Rhodium-Koordination ist bereits literaturbekannt. [21] Beide Heteroelement-NMR-Signalew urden bei hohen Frequenzen ( 119 Sn-NMR 8,3 112 ppm; 207 Pb-NMR 9, 11 269 ppm), verglichen mit bekannten Organometallostannylenen und -plumbylenen, gefunden. [7,17,18,22] Der kationische Komplex [Cp*W(CO) 3 Sn(NHC)][Al(OC(CF 3 ) 3 ) 4 ]weist ebenfalls eine 119 Sn-NMR-Resonanz bei sehr hohen Frequenzen auf (3318 ppm).…”