Di- and Zerovalent Platinaboratranes:  The First Pentacoordinate d¹⁰ Platinum(0) Complex

Abstract

The reaction of [PtCl 2 (PPh 3 ) 2 ] with Na[H-B(mt) 3 ] (mt ) methimazolyl) affords the platinaboratrane salt [PtH(PPh 3 ){B(mt) 3 }]Cl(Pt II fB), the first example of a metallaboratrane with the metal center in the +2 oxidation state. Base-induced dehydrochlorinationaffordsthefirstd 10 metallaboratrane,[Pt(PPh 3 ){B(mt) 3 }]-(Pt 0 fB), based on an unprecedented pentacoordinate platinum(0) geometry.

Reactivity of Lewis Basic Platinum Complexes Towards Fluoroboranes

“…[13] However, experimental proof for the existence of dative bonds between boranes and Lewis basic transition-metal complexes was disclosed several years later by Hill and coworkers with the synthesis of a supported borane adduct of ruthenium in which the Lewis acidic center is linked to the metal base by a supporting covalent scaffold (Figure 1, 4), [14] a concept that subsequently has been widely applied to many other borane complexes. [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] Nevertheless, we conducted further experiments in our laboratory aimed at the structural characterization of a complex with an unsupported bond between a borane and a Lewis basic transition metal. To this end, we investigated the well-established complex [PtA C H T U N G T R E N N U N G (PCy 3 ) 2 ] (5) in the presence of BF 3 .…”

Synthetic reactions and coordination modes of ruthenium complexes with tris(mercaptomethimazolyl)borate ligands

“…However, this simple analogy failed in the previous reports to prepare organometallic derivatives of the Tm R ligand [16][17][18]. Recently, Hill and co-workers have successfully reported this class of complexes to include examples based on osmium, rhodium, iridium, and platinum [19][20][21][22][23][24][25][26][27][28], while further examples based on iron, cobalt, rhodium, iridium, nickel, and palladium have been provided by the groups of Rabinovich [29], Tatsumi [11], Parkin [30][31][32] [17,18,35], and [RuH (CO)(PPh 3 )(Tm Me )] and [RuCl(dmso) 2 (Tm Me )] with a j 3 -H,S,S-Ru coordination mode [16,28], presumably bidentate coordination of Tm Me via two of its three sulfur donor atoms, which reveals an agostic BAHARu interaction [16,28]. We describe in this paper the [28,36], expand the pool of ruthenium-sulfur complexes with now available for the comparative study of their molecular structures and spectroscopic properties.…”

Crystal field arguments to explain the trans labilisation within transition metal–borane complexes

“…This has been shown in a large number of examples that have been reported over the past few years. The majority of compounds, which have been provided by Hill [2][3][4][5][6][7][8][9][10][11][12] and others [13][14][15][16][17][18][19][20][21], contain either the flexible scorpionate ligand, Tm [hydrotris(2-methyl-1-imidazolyl)borate] or similar derivatives (Fig. 2).…”