Transition metal catalyzed exchange of deuterium gas with terminal boron-hydrogen bonds in carboranes, metallocarboranes, and other boron compounds

A General, Rhodium‐Catalyzed, Synthesis of Deuterated Boranes and N‐Methyl Polyaminoboranes

“…AlthoughB H/BD exchange has been observedi nt ransition metal borane s-complexes, [15] examples of catalytic H/De xchange for the synthesis of deuterated boranes are scarce.E xamplesi nclude reaction of pinacol-or catecholborane with D 2 using [Ru(PCy 3 ) 2 H 2 (H 2 ) 2 ] [16] or [IrHCl{C(NtBuCH) 2 }{C(NtBuCH)-(CN(CCH 2 Me 2 )CH) 2 }] [17] catalysts; although the latter complex was also shown to be ineffective for deuteration of H 3 B·L (L = SMe 2 ,R N(CH 2 CH 2 ) 2 O, R = H, Me). H/D exchange of H 3 B·NMe 3 has been reported using aR uHCl(PPh 3 ) 3 catalyst, by bubbling D 2 throughat oluene solution at 100 8Cf or 24 hours, [18] but no comment as to the yield obtained was made.…”

Experimental Evidence Supporting Related Mechanisms for Ru(II)-Catalyzed Dehydrocoupling and Hydrolysis of Amine-Boranes

“…Nevertheless, blank experiments confirmed that, under our experimental conditions, in absence of catalysts, none of the substrates experienced H–D exchange at the terminal boron–hydrogen (see Figure S20 in SI), which confirms that the observed substrate-deuteration is a metal-catalyzed process. Deuterium exchange at B–H bonds of amine-borane adducts using several Ru, and Ir catalysts is a process known since the middle 70s, , but high temperatures and the use of D 2 gas as deuterium source were required. In 1999 Shimoi described a rhenium polyhydride-mediated deuteration of TMAB and H 3 N·PPh 3 by H–D exchange from C 6 D 6 .…”

Insertion of platinum into an ortho-carboranyl boron–hydrogen bond. The crystal and molecular structure of the diphenyl(ortho-carboranyl)-phosphine complex [PtCl(Ph2PC2B10H10)(Ph2PC2B10H11)]

“…Selected interatomic distances and angles (26) 1.775 (21) 1.800 (23) (h) Bond angles (") Cl-Pt-P( 1) 90.6( 1) C1-Pt-P( 2) 106.0( 1) C1-P t-B ( 1 ) 1 64.0( 3) Pt-P( 1 )-c ( 1) 120.6( 3) Pt-P(1)-C( 7) 117.7(3) Pt-P(1)-C (25) 93.2(3) C(l)-P(l)-C(7) 109.3(4) C(l)-P(l)-C (25) 107.2(5) C( 7)-P(l)-C (25) 106.1(4) P( 1)-C( 25)-C( 26) 107.3( 7)…”

“…111.4(6) P( 1 )-C (2 5)-B ( 1 0) 1 3 6.6 (8) Pt-B( 1)-C ( 25) 10 1.4( 6) Pt-B( 1)-C ( 26) 1 12.7 (7) Pt-B( 1)-B( 5 12)-B( 13) B( 12)-B( 14) B( 12)-B( 15) B( 13)-B (1 4) B( 13)-B( 15) B( 13)-B( 16) B( 1 3)-B( 18) B( 14)-B( 17 The P-C(pheny1) bond lengths are 1.783( 10)-1.829(7)…”