Syntheses and Structural Characterizations of Ferra- and Cobaltacarborane Complexes Derived from the arachno-6-R-5,6,7-C(3)B(7)H(12) [R- = NCCH(2)-, MeOC(O)CH(2)-, MeC(O)CH(2)-] Tricarbaborane(1).
A series of ferratricarbaboranyl complexes, closo-1-(eta-C(5)H(5))FeRC(3)B(7)H(9) [R- = H-, NCCH(2)-, MeOC(O)CH(2)-], have been generated by the reactions of (eta-C(5)H(5))Fe(CO)(2)I with tricarbaboranyl arachno-6-R-5,6,7-C(3)B(7)H(11)(-) anions. Structural characterizations of closo-1-(eta-C(5)H(5))Fe-2-(NCCH(2))-2,3,4-C(3)B(7)H(9), 1c, closo-1-(eta-C(5)H(5))Fe-3-(NCCH(2))-2,3,4-C(3)B(7)H(9), 1d, closo-1-(eta-C(5)H(5))Fe-2-(MeCH(3)OC(O)CH(2))-2,3,4-C(3)B(7)H(9), 2b, and closo-1-(eta-C(5)H(5))Fe-3-(MeOC(O)CH(2))-2,3,4-C(3)B(7)H(9), 2c, show the ferratricarbaboranyl cages in these complexes have closo-octadecahedral structures containing carbon atoms in the two four-coordinate positions closest to the iron. Other isolated products arise from further reactions of the side chain groups, with crystallographically characterized products including the multicage complex (&mgr;(2,12)(')-CH(2))[closo-1-(eta-C(5)H(5))Fe-2,3,4-C(3)B(7)H(9)][arachno-5'-(NCCH(2))-5',7',9',12',11'-C(4)NB(7)H(10)], 1e, and the first polyboron metallapentacarbaborane nido-2-(eta-C(5)H(5))Fe-7-Me-7,8,9,10,12-C(5)B(6)H(10), 3c. Cobaltatricarbaboranes of general formula 1-(eta-C(5)H(5))Co(NCCH(2))C(3)B(7)H(9), 4b-d, along with the unique multimetal cluster commo-Co-[closo-1-Co-8,9-((eta-C(5)H(5))Co)(2)-2,3,5-C(3)B(7)H(10)][closo-2'-Co-3'-(NCCH(2)CH(2))-1',10'-C(2)B(7)H(8)], 4e, were isolated from the reaction of cobalt chloride with a mixture of the arachno-6-NCCH(2)-5,6,7-C(3)B(7)H(11)(-) and cyclopentadienyl anions.
Barnum
Beverly A.
BA
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323.
Carroll
Patrick J.
PJ
Sneddon
Larry G.
LG