Synthesis of η-cyclopentadienyl-polyborane derivatives of molybdenum and tungsten

Substitution at boron in molybdaborane frameworks: Synthesis and characterization of isomeric (η5-C5Me5Mo)2B5HnXm (when X=Cl: n=5, 7, 8; m=4, 2, 1 and X=Me: n=6, 7; m=3, 2)

“…1. Its geometry is similar to that of (g 5 -C 5 Me 5 M) 2 B 5 H 9 , (M = Cr, Mo, W) [46][47][48] and is best described as a bicapped closo trigonal bipyramid. The Mo-Mo, avg.…”

Synthesis and crystal structures of two (cyclopentadienyl)titanium(III) hydroborate complexes, [Cp∗TiCl(BH4)]2 and Cp2Ti(B3H8)

“…We can find only one similar reaction, in which ''B 3 H 7 " prepared in situ reacts with a transition metal complex to form a metal BH 4 product [14]. A few examples of the reverse reaction have been described: [Mo(CO) 4 (B 3 H 8 ) À ] [15], Cp * ReH 3 (B 3 H 8 ) [16], and WH 3 (B 3 H 8 [17] have been prepared by treating [Mo 2 H(CO) 10 À ], Cp * ReH 6 , and WH 6 (PMe 3 ) 3 with BH 3 Á thf, respectively, and (C 5 H 4 -i-Pr)WH 3 (B 3 H 8 ) has been made by treating (C 5 H 4 -i-Pr)WCl 4 with LiBH 4 [18]. In addition, other B 3 H x fragments (especially those with x = 6 or 7) can be made by adding BH 3 to a transition metal hydride or chloride [19][20][21][22][23][24][25][26][27][28].…”

Fine Tuning of Metallaborane Geometries: Chemistry of Metallaboranes of Early Transition Metals Derived from Metal Halides and Monoborane Reagents

“…[1] The development of metallaborane chemistry has followed a similar pathway, with new species often obtained from conditions that favor the thermodynamic product, either through thermolysis or by simple metathesis reactions between a preformed polyborane anion and transition-metal halides. [2][3][4][5] Detailed investigations of the Co, [6] Rh, [7] Ir, [8,9] Fe, [10] Ru, [11] Re, [12,13] Cr, [14,15] Mo, [10,[16][17][18] W, [10,19,20] and Ta [21][22][23] systems reported to date reveal that metal identity affects products. For example, the earlier transition metals facilitate dehydrogenation leading to highly condensed clusters, such as closo-A C H T U N G -T R E N N U N G [(Cp*M) 2 B n H n + m ], (M = Re: [13] n = 7-10, m = 0; M = W: [12] n = 7, m = 2), whereas late transition elements form stable nido-or arachno-metallaboranes, such as nido-[(Cp*Ru) 2 B 10 H 16 ] [24] or arachno-1-[(Cp*IrH)B 4 H 9 ].…”