A metathesis reaction of [Cp*IrCl2]2 with butadienesulfinate lithium (SO2CHCRCHCHR)Li (R = H, 1Li; Me, 2Li) affords the dinuclear compounds [Cp*Ir(Cl)2{(5-η)-SO2CHCRCHCHR}(Li)(THF)]2 (R = H, 3; Me, 4), respectively. The single-crystal X-ray analysis of 3 and 4 reveals the presence of metallacyclic, five- and eight-membered rings, which easily break to afford compounds Cp*IrCl[(1,2,5-η)-SO2CHCRCHCHR] [R = H, (5), Me (6)], upon displacement of THF and LiCl. The 1H and 13C NMR data are consistent with the single-crystal X-ray diffraction structures of 3 and 4. Compounds 5 and 6 showed that the butadienesulfonyl ligands are coordinated through the sulfur atoms and the terminal double bonds, according to the X-ray study of compound 5 and NMR spectroscopy. Immediate formation of compound 5 can be achieved in 83% yield from [Cp*IrCl2]2 and 1K, showing that the alkaline metal is crucial in the isolation of the lithium derivatives 3 and 4.

The systematic exploration of the synthesis of heteropentadienyl metal complexes leads us to study the metathesis reaction of [(η 4 -COD)Ir(μ 2 -Cl)] 2 with lithium 2,4-dimethyloxopentadienide, which affords the dinuclear Ir 0 −Ir II compound (η 4 -COD)Ir[η 1:1 -μ 2 -η 4 -CHC(Me)CHC(Me)O)]-Ir(η 4 -COD) (1) with a metal−metal bond. The COD ligands are coordinated η 4 to each Ir center, whereas the oxopentadienyl ligand is bridging both Ir atoms, allowing the formation of a novel iridapyran complex with Ir II and bonding η 4 with Ir 0

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Powder diffraction pattern for KCl and TGA compound 11. Crystal Structures Compounds Refinement details :Program used SHELXL-97 (Sheldrick 1997) CifRtf version used 2.0122.6( 7) C(3)-C(4)-S(1) 119.8(6) C(10)-C(9)-C(8) 122.3(7) C(10)-C(9)-Ir(1) 72.2(4) C(8)-C(9)-Ir(1) 110.4(5) C(9)-C(10)-C(11) 123.4(7) C(9)-C(10)-Ir(1) 70.4(4) C(11)-C(10)-Ir(1) 113.8(5) C(12)-C(11)-C(10)113.5( 6) C( 11)-C( 12)-C( 5) 112.6( 6) C( 6)-C(5)-C( 12)124.4( 7) C( 6)-C( 5)-Ir(1) 70.6(4) C( 12)-C(5)-Ir(1) 114.0(5) C( 5)-C( 6)-C( 7) 121.7( 7) C( 5)-C(6)-Ir(1) 69.9(4) C( 7)-C( 6)-Ir( 1) 114.1(5) C(6)-C(7)-C(8) 113.4(6) C(9)-C(8)-C(7) 114.0(6) C(5)-Ir(1)-C(1) 139.1(3) C(5)-Ir(1)-C(6) 39.5(3) C(1)-Ir(1)-C(6) 175.3(3) C(5)-Ir(1)-C(2) 101.4(3) C(1)-Ir(1)-C(2) 38.5(3) C(6)-Ir(1)-C(2) 140.9(3) C(5)-Ir(1)-C(9) 95.9(3) C(1)-Ir(1)-C(9) 95.0(3) C(6)-Ir(1)-C(9) 81.1(3) C(2)-Ir(1)-C(9) 112.7(3) C(5)-Ir(1)-C(10) 78.7(3) C(1)-Ir(1)-C(10) 86.7(3) C(6)-Ir(1)-C(10) 88.6(3) C(2)-Ir(1)-C(10) 83.9(3) C(9)-Ir(1)-C(10) 37.4(3) C(5)-Ir(1)-S(1) 87.0(2) C(1)-Ir(1)-S(1) 93.8(2) C(6)-Ir(1)-S(1) 90.6(2) C(2)-Ir(1)-S(1) 83.1(2) C(9)-Ir(1)-S(1) 162.8(2) C(10)-Ir(1)-S(1) 158.4(2) C(5)-Ir(1)-S(1A) 136.9(2) C(1)-Ir(1)-S(1A) 82.8(2) C(6)-Ir(1)-S(1A) 99.6(2) C(2)-Ir(1)-S(1A) 116.8(2) C(9)-Ir(1)-S(1A) 87.5(2) C(10)-Ir(1)-S(1A) 122.4(2) S(1)-Ir(1)-S(1A) 79.01(6) C(4)-S(1)-Ir(1) 99.8(3) C(4)-S(1)-Ir(1A) 118.2(3) Ir(1)-S(1)-Ir(1A) 100.99(6) ________________________________________________________________ Symmetry operations used for equivalent atoms : ..A : -x, -y, -zTable. Crystal Data and Data Collection Parameters: Compound 5 Chem. formula C 24 H 34 Ir 2 S 2 Form. wght. 771.03 Cryst. size [mm] 0.08 x 0.15 x 0.17 Cryst. system triclinic Space group P-1 a, [Å] 6.9771(2) b, [Å] 7.6804(2) c, [Å] 10.9819(3) α, [°] 108.7530(1) β, [°]

Reactions of aqueous base with the dicationic iridium and rhodium thiophene complexes [Cp*Ir(η5-2,5-Me2T)](X)2 (X = BF4, 1(BF 4 ); X = OSO2CF3, 1(OTf)) and [Cp*Rh(η5-2,5-Me2T)](BF4)2 (8(BF 4 )) and the acid/base reactivity of these products are discussed. The reaction of 1(BF 4 ) with 1 equiv of aqueous KOH (0.01 M) affords the following mixture of mono-, di-, and tetranuclear compounds:  [Cp*Ir(η4-SC(Me)CHCHC(O)Me)] (3), (Cp*Ir)[Cp*Ir(η4-SC(Me)CHCHC(O)Me)]3(BF4)2 (4(BF 4 )), [(Cp*Ir)2(μ2,η4-SC(Me)CHCC(O)Me)](BF4) (5(BF 4 )), and [Cp*Ir(μ2,η3-SC(Me)CHCH2C(O)Me)]2(BF4)2 (6(BF 4 )). The 1H and 13C NMR data are consistent with the single-crystal X-ray diffraction structures of the cationic complexes 4(BF 4 ), 5(OTf), and 6(BF 4 ). These products are formed by a complex series of reactions that begin with the displacement of the 2,5-dimethylthiophene (2,5-Me2T) ligand from 1 and reaction of the resulting “[Cp*Ir]2+” fragment with 3. In the synthesis of 8(BF 4 ), the new complex [(Cp*Rh)2(μ2,η4-SC(Me)CHCC(O)Me)](BF4) (9(BF 4 )), analogous to 5(BF 4 ), is produced. Studies of the reactions of [Cp*Rh(η5-2,5-Me2T)](BF4)2 (8(BF 4 )) with OH- and MeO- show a type of reactivity quite different from that observed for 1(BF 4 ) and 1(OTf). The solvolysis of 8(BF 4 ) in acetone affords the mononuclear complex [Cp*Rh(OCMe2)2(OH)](BF4) (10(BF 4 )), whose crystal structure is described. Detailed NMR studies establish the pathways by which [Cp*Ir(η5-2,5-Me2T)]2+ (1) and [Cp*Rh(η5-2,5-Me2T)]2+ (8) react with H2O/OH- and MeOH/MeO- to give the variety of observed products.