Some reactions of [Os3(CO)10(NCMe)2] with arenes; the molecular structure of [Os3H2(CO)9(C6H4)]

The activation and transformations of acenaphthylene by osmium carbonyl cluster complexes

“…From the coalescence temperature we have calculated the free energy of activation for the exchange process, DG % 268 0 11:2 kcal mol (1 . These properties are similar to that of the known osmiumÁ/benzyne complex Os 3 (CO) 9 (m-H) 2 (C 6 H 4 ) [8]. Compound 3 is formed from 2 by the loss of one CO ligand and the cleavage of the alkenyl C Ã/H bond, and thus requires a higher temperature (80 8C) and longer reaction time (2 h) (see Scheme 1).…”

“…These ligands can be formed by cleavage of hydrogen atoms or substituents from substituted phenyl rings [7 Á/15]. Arynes stabilized by osmium cluster compounds include Os 3 (CO) 9 (m 3 Á/h 2 -C 6 H 4 ) [8], Os 4 (CO) 12 (m 4 Á/h 2 :h 2 -C 6 H 4 Ã/C 6 H 5 ), and Os 2 (CO) 6 (m Á/h 4 -C 12 H 10 ) [9], (see Fig. 1).…”

Isolation and X-ray structure determination of [Os4(CO)12(C9H6)], an indyne‘butterfly’ cluster

“…Bond lengths: Os(l)-Os(2) 2.747(3), Os(l)-Os(3) 2.737(2), OS( 2 ) -0 ~( 3) 2.883( 3), OS( 2)-0~(4) 2.735( 3), 0 ~( 3 ) -0 ~( 4 ) 2.760( 3), OS(1)-C(l) 2.28(3), Os(l)-C(2) 2.25(3), 0~(2)-C(2) 2.08(3), Os(3)-C(l) 2.19(3), 0~(4)-C(l) 2.23(3), 0~(4)-C(2) 2.25(3), C(l)-C(2) 1.47(5), C( 1)-C(5) 1.40(5), C(2)-C(3) 1.65(4), C(3)-C(4) 1.48(5), C(4)-C(5) 1.41(4), C(4)-C(6) 1.24(5), C(5)-C(9) 1.47(4), C(6)-C(7) 0 ~( 2 ) -0 ~( 1)-0~(3) 63.4( l ) , 0 ~( 1 ) -0 ~( 2 ) -0 ~( 3 ) 58.1( l), Os(1)-0 ~( 2 ) -0 ~( 4 ) 92.5(1), 0 ~( 3 ) -0 ~( 2 ) -0 ~( 4 ) 58.8( l), 0 ~( 1 ) -0 ~( 3 ) -Os(2) 58.5(1), 0 ~( 1 ) -0 ~( 3 ) -0 ~( 4 ) 92.2(1), 0 ~( 2 ) -0 ~( 3 ) -0 ~( 4 ) 57.9( l ) , 0 ~( 2 ) -0 ~( 4 ) -0 ~( 3 ) 63.3( 1), OS( 1)-C( 1)-0~(3) 75.7( lo), O~(l)-C(l)-0~(4) 123.3(16), 0~(3)-C(1)-0~(4) 77.5( l l ) , Os(1)-C(1)-C(2) 70.2(16), 0~(3)-C(l)-C(2) 107.2(22), 0~(4)-C(l)-C(2) 71.6(17), Os(l)-C(l)-C(5) 116.8(2), 0~(3)-C(l)-C(5) 142.2(25), Os(4)-C( 1)-C( 5 ) 115.0(21), C( 2)-C( 1)-C(5) 110.6( 27), OS( 1)-C(2)-Os(2) 78.6(10), O~(l)-C(2)-0~(4) 123.4(13), 0~(3)-C(2)-0~(4) 78.2(9), OS( 1)-C(2)-C( 1) 71.9( 16), 0~(2)-C(2)-C( 1) 11 1.5(21), 0~(4)-C(2)-C(l) 70.0(15), Os(l)-C(2)-C(3) 112.9(18), 0~(2)-C(2)-C(3) 146.2(21). 0~(4)-C(2)-C(3) 115.1( 18), C(l)-C(2)-C(3)1.37(7), C(7)-C(8) 1.50(7), C(8)-C(9) 1.27(6) A; bond angles:…”

Opening of Carborane Cages by Metal Cluster Complexes: The Reaction of a Thiolate-Substituted Carborane with Triosmium Carbonyl Cluster Complexes

“…A total of 20.0 mg (0.019 mmol) of compound 1 was added to a solution of 44.0 mg (0.047 mmol) of Os 3 (CO) 10 (NCMe) 2 in 30 mL of toluene, and the solution was heated to reflux for 8 h. The solvent was then removed in vacuo and the products were isolated by TLC on silica by using hexane as the eluent. In order of elution, they were 7.7 mg of Os 3 (CO) 12 , 14.1 mg of 2 (39%), 1.7 mg of Os 3 (CO) 10 (μ-OH)­(μ-H), 7.3 mg of Os 3 (CO) 9 ((μ 3 -C 6 H 3 Me)­(μ-H), and 1.7 mg of Os 3 (CO) 10 (μ-H) 2 . Compound 2 could also be obtained, albeit at a low yield (2%) by refluxing 1 in nonane for 3.5 h. Spectral data for 2 , IR (υ CO , cm –1 , in hexane): 2112 (m), 2092 (vs), 2075 (vs), 2065 (s), 2052­(vs), 2029 (sh, m), 2025 (vs), 2016 (w), 2004 (m), 1996 (w), 1985 (w), 1974 (w).…”