Interaction between d‐ and p‐Block Metals: Synthesis and Structure of Platinum–Alane Adducts

Abstract

Dative bonds between transition metals and the archetypal Lewis acid BF 3 were proposed as early as 1966, [1] but were called into question 30 years later.[2] However, more recent work by Hill, [3] Parkin, [4] Bourissou, [5] and Rabinovich [6] and respective co-workers has demonstrated that borane complexes of the type [L n M À BR 3 ] [7] can be obtained from a range of late Lewis basic transition metals, and the nature of the dative metal-boron bond has been elucidated by experimental and computational studies. In addition, the metal-phosphine fragments {M(PCy 3 )} (M = Pd, Pt) have proven to act as versatile metal bases towards a range of coordinated boryl [8] and borylene ligands. [9] The heavier Group 13 elements are also known to form a variety of transition-metal complexes, in analogy to boron.[10]

Silver(i) and thallium(i) cations as unsupported bridges between two metal bases

“…The 195 Pt{ 1 H} NMR spectra of the complexes 3 (δ = -4853 ppm) and 4 (δ = -4697 ppm) reveal a large down-field shift compared to the starting material 1 (δ = -6501 ppm). 43 These findings are in good agreement with analogous neutral MOLPs from our group. 43,44,47 Single crystals of 3 and 4 suitable for X-ray diffraction were obtained by slow evaporation from thf at -30 °C.…”

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

“…The transition metal precursors can be readily synthesized from Vaska's complex, [Ir(PPh 3 ) 2 (Cl)(CO)] (5) and its rhodium analogue Rh(PPh 3 ) 2 (Cl)(CO) (6). [46] Iridium and Rhodium complexes 7, 8, 9, and 10 have been fully characterized by NMR and IR spectroscopy, as well as elemental analysis.…”

“…[1][2][3][4][5] As a complement to the ongoing work encompassing transition metal systems, our lab is interested in exploring the rich chemistry of heterobimetallic complexes involving a transition metal and a main group element, primarily aluminum. 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.…”

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

“…The Z-type ligands in the so-formed T-shape, tri-coordinate complexes include BeCl 2 [328] (Fig. 60, center top), AlCl 3 [329][330][331], GaCl 3 [332] (Fig. 60, center bottom), and ZrCl 4 [333].…”