Reactions of cis and trans Bcat, Aryl Osmium Complexes (cat = 1,2-O2C6H4). Bis(Bcat) Complexes of Osmium and Ruthenium and a Structural Comparison of
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Reaction of Os(Bcat)Cl(CO)(PPh3)2 (1) (HBcat = catecholborane or 1,3,2-benzodioxaborole)with o-tolyllithium gives the yellow, five-coordinate Bcat, aryl complex Os(Bcat)(o-tolyl)(CO)(PPh3)2 (2). Treatment of 2 with carbon monoxide or p-tolylisocyanide gives thecorresponding saturated Bcat, aryl complexes cis-Os(Bcat)(o-tolyl)(CO)2(PPh3)2 (3) and cis-Os(Bcat)(o-tolyl)(CO)(CN-p-tolyl)(PPh3)2 (4). Complexes 3 and 4 decompose in benzenesolution at room temperature to give o-tolylBcat and the orthometalated triphenylphosphinecomplexes Os(C6H4PPh2)H(CO)2(PPh3) (5) and Os(C6H4PPh2)H(CO)(CN-p-tolyl)(PPh3) (as amixture of two isomers, 6a and 6b), respectively. In the presence of B2cat2, 3 and 4 react togive the bis(Bcat) complexes Os(Bcat)2(CO)2(PPh3)2 (7) and Os(Bcat)2(CO)(CN-p-tolyl)(PPh3)2(8). Complex 3 also reacts with HBcat to produce Os(Bcat)H(CO)2(PPh3)2 (9). The bis(Bcat)ruthenium complexes Ru(Bcat)2(CO)2(PPh3)2 (10) and Ru(Bcat)2(CO)(CN-p-tolyl)(PPh3)2 (11)can be prepared by treatment of Ru(CO)2(PPh3)3 or Ru(CO)(CN-p-tolyl)(PPh3)3 with B2cat2.Complex 3 reacts with Cl2C=CCl2 or CHCl3 to produce OsCl(CCl=CCl2)(CO)2(PPh3)2 (12) orOsCl2(CO)2(PPh3)2, respectively. Complex 1 when treated with CO gives cis-Os(Bcat)Cl(CO)2(PPh3)2 (13), which in turn with phenyllithium or o-tolyllithium gives trans-Os(Bcat)(Ph)(CO)2(PPh3)2 (14) or trans-Os(Bcat)(o-tolyl)(CO)2(PPh3)2 (15). Complex 15 reacts with I2 togive a mixture of trans-Os(Bcat)I(CO)2(PPh3)2 (16) and trans-Os(o-tolyl)I(CO)2(PPh3)2 (17).Complex 16 is also formed by heating cis-Os(Bcat)I(CO)2(PPh3)2 (18) in benzene. Crystalstructures of complexes, 5, 8, 10, 11, 12, 16, and 18 are reported.

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