Reactions of the η5-2,5-dimethylthiophene complex Cp∗Ir(η5-2,5-Me2T)2+ with nucleophiles (Ph−, Me−, −CH(CO2Me)2 and OH−)1

Chen, Jiabi; Su, Y.; Jacobson, R. A.; Angelici, Robert J.

doi:10.1016/0022-328x(95)06031-q

Cited by 14 publications

(13 citation statements)

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“…Thus, - CH(CO 2 Me) 2 and cyclopentadienide react to give the products shown in eqs 32 94 and 33 . The acidic protons in the proposed intermediates are removed by a second mole of nucleophile to give the products, whose structures were established crystallographically and are very similar to that of the related acylthiolate Cp*Ir(η 4 -SC 3 H 2 MeC(O)Me) . In a quite different type of reaction with a nucleophile, Cp*Ir(η 5 -T) 2+ reacts with PMe 3 , PPh 2 Me, and PPh 3 to give Cp*Ir(η 4 -T·PR 3 ) 2+ , in which PR 3 is proposed to have added to C-2, as in (OC) 3 Mn(η 4 -T·Nuc) + ( 42 ) …”

Section: Reactions Of η5-thiophene Complexes With Nucleophilesmentioning

confidence: 90%

“…Although studied less extensively than the Cp‘Rh(η 5 -Me 4 T) 2+ system, Cp*Ir(η 5 -2,5-Me 2 T) 2+ also reacts rapidly with OH - to give both the S-oxide Cp*Ir(η 5 -2,5-Me 2 T·O), analogous to 48 , and the acythiolate Cp*Ir(η 4 -SC 3 H 2 MeC(O)Me), whose structure was shown by X-ray studies to have an anti acyl group, as in structure 51 , rather than a syn acyl as found in Cp*Rh(η 4 -SC 3 Me 3 C(O)Me) . The Cp*Ir(η 4 -SC 3 H 2 MeC(O)Me) acythiolate is also obtained unexpectedly in the reaction of Cp*Ir(η 5 -2,5-Me 2 T) 2+ with PhLi in THF, along with Cp*Ir(2,5-Me 2 T·2Ph), which was not structurally characterized.…”

Section: Reactions Of η5-thiophene Complexes With Nucleophilesmentioning

confidence: 99%

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Thiophenes in Organotransition Metal Chemistry: Patterns of Reactivity

Angelici

2001

Organometallics

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Thiophenes, including benzothiophenes and dibenzothiophenes, undergo a variety of reactions with transition metal complexes that lead to products in which the thiophene is partially reduced or cleaved at a C−S bond. The specific types of reactivity depend on the modes of thiophene coordination to the metal, which in turn depend on the particular metal and its associated ligands. It is the intent of this review to organize these numerous reactions of thiophenes into categories that illustrate distinct patterns of reactivity. It is hoped that an understanding of such patterns will stimulate the use of thiophene−organotransition metal chemistry in synthetic organic chemistry.

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Section: Reactions Of η5-thiophene Complexes With Nucleophilesmentioning

confidence: 90%

Section: Reactions Of η5-thiophene Complexes With Nucleophilesmentioning

confidence: 99%

Thiophenes in Organotransition Metal Chemistry: Patterns of Reactivity

Angelici

2001

Organometallics

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154

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“…Reactions of aqueous base with the dicationic iridium thiophene complex [Cp*Ir(2,5-dimethyl-η 5 -thiophene)][X] 2 (X = BF 4 , OTf) afford a mixture of mono-, di-, and tetranuclear compounds [Cp*Ir(η 4 -SC(Me)CHCHC(O)Me)] (D), [(Cp*Ir) 2 (μ 2 ,η 4 -SC(Me)CHCHC(O)Me)](BF 4 ) (E), [Cp*Ir(μ 2 ,η 3 -SC(Me)CHCH 2 C(O)Me)] 2 (BF 4 ) 2 (F), and (Cp*Ir)[Cp*Ir(η 4 -SC(Me)CHCHC(O)Me)] 3 (BF 4 ) 2 (G) . The mononuclear acylthiolate complex [Cp*Ir(η 4 -SC(Me)CHCHC(O)Me)] (D) was also reported from the reaction of [Cp*Ir(2,5-dimethyl-η 5 -thiophene)][BF 4 ] 2 with PhLi in THF or ( n -Bu) 4 N + OH – in MeCN, and the dicationic thiophene complex readily adds secondary amines to afford [Cp*Ir(η 4 -SC(Me)CHCHC(Me)(N(CH 2 ) n )](BF 4 ) ( n = 4, 5) (H) …”

Section: Introductionmentioning

confidence: 99%

Chemistry of Iridium(I) Cyclooctadiene Compounds with Thiapentadienyl, Sulfinylpentadienyl, and Butadienesulfonyl Ligands

Gamero‐Melo

Melo-Trejo²,

Cervantes-Vásquez³

et al. 2011

Organometallics

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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, [°]

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“…From the first fraction, 0.006 g (20%, based on 3 ) of 2 was obtained. From the yellow fraction, 0.010 g (32%, based on 3 ) of yellow crystalline 22 was obtained (mp 131−132 °C dec). IR (CH 2 Cl 2 ): ν(CO) 1655 (s) cm -1 .…”

Section: Methodsmentioning

confidence: 99%

Syntheses, Structures, and Reactions of η⁶Complexes of Iridathiabenzene with Chromium, Molybdenum, and Tungsten Carbonyls

2002

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The iridathiabenzene analogues [η6-Cp*Ir(C,S-2,5-Me2T)]M(CO)3, where M = Cr (3), Mo (5), W (7), of (η6-arene)M(CO)3 are prepared from M(CO)3(NCMe)3 and Cp*Ir(C,S-2,5-Me2T) (2), where C,S-2,5-Me2T is ring-opened 2,5-dimethylthiophene. The high reactivity and coordination flexibility of the η6-Cp*Ir(C,S-2,5-Me2T) ligand leads to a variety of products upon reaction with phosphine ligands. The reaction of 3 with PEt3 leads to PEt3 adduct formation at the Ir in the product [η5-Cp*Ir(PEt3)(C,S-2,5-Me2T)][Cr(CO)3] (17). On the other hand, reaction of the analogous tungsten complex 7 with PEt3 yields the adduct [η4-Cp*Ir(C,S-2,5-Me2T)]W(CO)2(PEt3)(μ-CO) (19), in which PEt3 adds to the W atom. These and other studies show that the iridathiabenzene ligand is capable of coordination to Cr, Mo, or W through one, four, five, or six of its ring atoms. When 7 is reacted with CF3SO3H, protonation occurs at the tungsten, as occurs in the protonation of the analogous arene complex (η6-C6Me6)W(CO)3. Structures of four of the complexes were established by X-ray studies.

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Reactions of the η5-2,5-dimethylthiophene complex Cp∗Ir(η5-2,5-Me2T)2+ with nucleophiles (Ph−, Me−, −CH(CO2Me)2 and OH−)1

Cited by 14 publications

References 20 publications

Thiophenes in Organotransition Metal Chemistry: Patterns of Reactivity

Thiophenes in Organotransition Metal Chemistry: Patterns of Reactivity

Chemistry of Iridium(I) Cyclooctadiene Compounds with Thiapentadienyl, Sulfinylpentadienyl, and Butadienesulfonyl Ligands

Syntheses, Structures, and Reactions of η⁶Complexes of Iridathiabenzene with Chromium, Molybdenum, and Tungsten Carbonyls

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Reactions of the η5-2,5-dimethylthiophene complex Cp∗Ir(η5-2,5-Me2T)2+ with nucleophiles (Ph−, Me−, −CH(CO2Me)2 and OH−)1

Cited by 14 publications

References 20 publications

Thiophenes in Organotransition Metal Chemistry: Patterns of Reactivity

Thiophenes in Organotransition Metal Chemistry: Patterns of Reactivity

Chemistry of Iridium(I) Cyclooctadiene Compounds with Thiapentadienyl, Sulfinylpentadienyl, and Butadienesulfonyl Ligands

Syntheses, Structures, and Reactions of η6Complexes of Iridathiabenzene with Chromium, Molybdenum, and Tungsten Carbonyls

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Syntheses, Structures, and Reactions of η⁶Complexes of Iridathiabenzene with Chromium, Molybdenum, and Tungsten Carbonyls