Synthesis and Platinum Complexes of an Alane‐Appended 1,1′‐Bis(phosphino)ferrocene Ligand

Abstract

An aryldimethylalane-appended analogue of 1,1'-bis(diphenylphosphino)ferrocene, FcPPAl, was prepared, and reaction with [Pt(nb)3 ] (nb=norbornene) afforded [Pt(η(2) -nb)(FcPPAl)] (1). Heating a solution of 1 to 80 °C resulted in crystallization of [{Pt(FcPPAl)}2 ] (2), whereas treatment of 1 with C2 H4 , C2 Ph2 , H2 , or CO provided [PtL(FcPPAl)] [L=C2 H4 (3), C2 Ph2 (4)], [PtH2 (FcPPAl)] (5), and [Pt(CO)(FcPPAl)] (6). In all complexes, the FcPPAl ligand is coordinated through both phosphines and the alane. Whereas 2 adopts a T-shaped geometry at platinum, 3-5 are square-pyramidal, and 6 is distorted square-planar. The hydride and carbonyl complexes feature unusual multicenter bonding involving platinum, aluminum, and a hydride or carbonyl ligand.

Functional group migrations between boron and metal centres within transition metal–borane and –boryl complexes and cleavage of H–H, E–H and E–E′ bonds

“…Interestingly, a related alane system has recently been reported by Emslie using the ligand FcPPAl. 65 In this case, upon addition of H 2 , two terminal hydride ligands are formed on the corresponding platinum complex and no significant interaction was observed between the aluminium centre and neither of the terminally coordinated hydrides. Furthermore, the addition of H 2 to the complex was not reversible even at elevated temperatures.…”

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

“…S1, ESI † ). 46 , 84 For example, 41 is formed upon hydrogenation of a Pt···norbornadiene precursor; it is currently unclear if the Pt→Al moiety plays a role in dihydrogen activation ( Fig. 10 ).…”

Synthesis and Electronic Characterization of Iridium‐Aluminum and Rhodium‐Aluminum Heterobimetallic Complexes Bridged by 3‐Oxypyridine and 4‐Oxypyridine

“…While analogous transitional metal-boron complexes have been studied extensively, [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] transition metal-aluminum heterobimetallics remain only sparsely investigated. [22][23][24][25][26][27][28][29][30][31][32][33][34] Aluminum is, however, of considerable interest as it is a potent Lewis acid and the most electropositive Group 13 element. Of the small pool of known aluminum-containing heterobimetallics, many of them incorporate early transition metals for applications in olefin polymerization.…”