TY - JOUR
T1 - Indenyl Carbametallaboranes III. The Synthesis and Characterisation of Novel Rhodium Carbaborane Compounds with 3-(C2B9)-8-{(C9H6)Rh(C9H7)}-3,1,2-closo-RhC2B9, 10-{(C9H6)Rh(C9H7)}-7,8-nido-C2B9, 9-{(C9H6)Rh(C9H7)}-7,8-nido-C2B9 and 3-(η-C9H7)-3,1,2-closo-RhC2B9 Structures
AU - Lewis, Zoë G.
AU - Welch, Alan J.
PY - 1992/10/20
Y1 - 1992/10/20
N2 - Title full: Indenyl carbametallaboranes. III. The synthesis and characterization of novel rhodium carbaborane compounds with 3-(C2B9)-8-(C9H6)Rh(C9 H7)-3,1,2-closo-RhC2B9, 10-(C9H6)Rh(C9H7)-7,8-nido-C 2B9, 9-(C9H6)Rh(C9H7)-7, 8-nido-C2B9 and 3-(η-C9H7)-3,1,2-closo-RhC2B 9 structures. When RhCl3·.3H2O and indene are refluxed in methanol a brown solid, [(C9H7)RhCl2]x, is deposited. This, in turn, reacts with a suspension of Tl2[7,8-nido-C2B9H11 in CH2Cl2 to afford three products, 3-(C2B9H11)-8-(C9H 6)Rh(C9H7)-3,1,2-closo-RhC2 B9 H10 (Ia), 10-(C9H6)Rh(C9H7)-7,8-nido-C 2B9H11 (IIa) and 9-(C9H6) Rh(C9H7)-7,8-nido-C2B9H 11 (IIIa). In Ia, which was characterized spectroscopically and crystallographically, a closo-(C2B9H11)Rh(C2B9 H10) fragment is bonded to a (C9H6)Rh(C9H7) fragment via a B(8)C bond, whereas in IIa and IIIa, which were characterized spectroscopically, the same organometallic fragment is linked to, respectively, B(10) and B(9) of a 7,8-nido-C2B9H11 unit. Reaction of [(C9H7)RhCl2]x with Tl2[7-(CH2OCH3)-7,8-nido-C2B 9H10] gives rise to a single isolatable product of 7-CH2OCH3-10-(C9H6)Rh(C 9H7)}-7, 8-nido-C2B9H10 (IIb) shown to be a simple analogue of IIa by NMR spectroscopic study. An analogue of IIIa, namely 7-Ph-9/11-(C9H6)Rh(C9H7)-7,8 -nido-C2 B9H10 (IIId) is one of the two products isolated following the reaction between [(C9H7) RhCl2]x and Tl2[7-Ph-7,8-nido-C2B9H10, the other being the closo carbametallaborane, 1-Ph-3-(C9H7)-3,1,2-closo-RhC2B9 H10 (IVd) characterized by unit cell and space group determination. A structural analogue, 1,2-(CH2OCH3)2- 3-(C9H7)-3,1,2-closo-RhC2B9H 9 (IVc) is the only product isolated from the reaction of [(C9H7)RhCl2]x with Tl2[7,8-(CH2OCH3)2-7,8-nido- C2B9H9]. The structural characterization of each of these novel rhodium carbaborane species is discussed, and the implications of their structures on the nature of [(C9H7)RhCl2]x is considered.
AB - Title full: Indenyl carbametallaboranes. III. The synthesis and characterization of novel rhodium carbaborane compounds with 3-(C2B9)-8-(C9H6)Rh(C9 H7)-3,1,2-closo-RhC2B9, 10-(C9H6)Rh(C9H7)-7,8-nido-C 2B9, 9-(C9H6)Rh(C9H7)-7, 8-nido-C2B9 and 3-(η-C9H7)-3,1,2-closo-RhC2B 9 structures. When RhCl3·.3H2O and indene are refluxed in methanol a brown solid, [(C9H7)RhCl2]x, is deposited. This, in turn, reacts with a suspension of Tl2[7,8-nido-C2B9H11 in CH2Cl2 to afford three products, 3-(C2B9H11)-8-(C9H 6)Rh(C9H7)-3,1,2-closo-RhC2 B9 H10 (Ia), 10-(C9H6)Rh(C9H7)-7,8-nido-C 2B9H11 (IIa) and 9-(C9H6) Rh(C9H7)-7,8-nido-C2B9H 11 (IIIa). In Ia, which was characterized spectroscopically and crystallographically, a closo-(C2B9H11)Rh(C2B9 H10) fragment is bonded to a (C9H6)Rh(C9H7) fragment via a B(8)C bond, whereas in IIa and IIIa, which were characterized spectroscopically, the same organometallic fragment is linked to, respectively, B(10) and B(9) of a 7,8-nido-C2B9H11 unit. Reaction of [(C9H7)RhCl2]x with Tl2[7-(CH2OCH3)-7,8-nido-C2B 9H10] gives rise to a single isolatable product of 7-CH2OCH3-10-(C9H6)Rh(C 9H7)}-7, 8-nido-C2B9H10 (IIb) shown to be a simple analogue of IIa by NMR spectroscopic study. An analogue of IIIa, namely 7-Ph-9/11-(C9H6)Rh(C9H7)-7,8 -nido-C2 B9H10 (IIId) is one of the two products isolated following the reaction between [(C9H7) RhCl2]x and Tl2[7-Ph-7,8-nido-C2B9H10, the other being the closo carbametallaborane, 1-Ph-3-(C9H7)-3,1,2-closo-RhC2B9 H10 (IVd) characterized by unit cell and space group determination. A structural analogue, 1,2-(CH2OCH3)2- 3-(C9H7)-3,1,2-closo-RhC2B9H 9 (IVc) is the only product isolated from the reaction of [(C9H7)RhCl2]x with Tl2[7,8-(CH2OCH3)2-7,8-nido- C2B9H9]. The structural characterization of each of these novel rhodium carbaborane species is discussed, and the implications of their structures on the nature of [(C9H7)RhCl2]x is considered.
UR - http://www.scopus.com/inward/record.url?scp=0011708629&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(92)83419-I
DO - 10.1016/0022-328X(92)83419-I
M3 - Article
AN - SCOPUS:0011708629
SN - 0022-328X
VL - 438
SP - 353
EP - 369
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 3
ER -