Mixed-Metal Cluster Chemistry. 23. Synthesis and Crystallographic and Electrochemical Studies of Alkyne-Coordinated Group 6-Iridium Clusters Linked by Heterocyclic Groups

Eleni G.A. Notaras; Nigel T. Lucas; Mark G. Humphrey; Anthony C. Willis; A. David Rae

doi:10.1021/om030253b

Mixed-Metal Cluster Chemistry. 23. Synthesis and Crystallographic and Electrochemical Studies of Alkyne-Coordinated Group 6-Iridium Clusters Linked by Heterocyclic Groups

Eleni G.A. Notaras, Nigel T. Lucas, Mark G. Humphrey^*, Anthony C. Willis, A. David Rae

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Abstract

Reaction between the tetrahedral cluster compound Mo₂Ir ₂(CO)₁₀(η⁵-C₅H ₄Me)₂ (1) and 2-iodo-5-(oct-1′-ynyl)thiophene afforded the pseudooctahedral cluster Mo₂Ir₂{U ₄-n²Me(CH₂₎₅C₂-5-C₄H ₂S-2-I}(CO)₈(n⁵-C₅H ₄Me)₂ (17) by formal insertion of the alkyne C≡C group into the Mo-Mo bond. Similar reactions of 1 or W₂Ir ₂(CO)₁₀(n⁵-C₅H₄Me) ₂ (2) with heterocyclic di- or triynes afforded the related mono-, di-, or tricluster compounds [M₂lr₂(CO)₈(n ⁵-C₅H₄Me)_2]2{u₈-n ⁴-Me(CH₂₎₅C₂-2-C₄H ₂-E-5-C₂(CH₂₎₅Me} [E = S, M = Mo (20), W (21); E = Se, M = Mo (30), W (31)], [M₂Ir₂(CO) ₈(n⁵-C₅H₄Me)₂] ₂{u₈n⁴-Me(CH₂₎₅C ₂-2-C₄H₂S-5-(E)-CH=CH-2C₄H ₂S-5-C₂(CH₂₎₅Me} [M = Mo (22), W (24)], M ₂Ir₂{u₄-n²-Me(CH₂₎₅C ₂-2-C₄-H₂S-5-(E)-CH=CH-2-C₄H ₂S-5-C≡C(CH₂₎₅Me}(CO)₈(n ⁵-C₅H₄Me)₂ [M = Mo (23), W (25)], [M₂Ir₂(CO)₈(n⁵C₅H ₄Me)_2]3{u₁₂-n⁶-Me(CH ₂₎₅C₂-2-C₄H₂S-5-C ₂-2-C₄H₂S-5-C₂(CH₂₎₅Me} [M = Mo (26), W(28)], and[M₂Ir₂(CO)₈(n ⁵-C₅H₄Me)_2]2{u₈-n ⁴-Me(CH₂₎₅C₂-2-C₄H ₂S-5-C₂-2-C₄H₂S-5-C≡C(CH ₂₎₅Me}[M = Mo (27), W (29)]. Compounds 27 and 29 correspond to the 1,2-dicluster adducts of the linear triyne Me(CH₂₎₅C=C-5-C ₄H₂S-2-C≡C-2-C₄H ₂S-5-C≡C(CH₂₎₅Me. No 1,3-dicluster isomer was isolated from direct reaction, but the molybdenum-containing 1,3-dicluster isomer was prepared by exploiting organic reaction chemistry on precoordinated functionalized alkyne ligands. Thus, Sonogashira coupling of 17 with trimethylsilylacetylene and subsequent desilylation gave Mo₂Ir ₂{u₄-n²-Me(CH₂₎₅C ₂-5-C₄H₂S-2-C≡CR}(CO)₈(n ⁵-C₅H₄Me)₂ [R = SiMe₃ (18), H (19)]. Sonogashira coupling of 17 and 19 gave the 1,3-isomer [Mo ₂Ir₂(CO)₈(n⁵-C₅H ₄Me)_2]2{u₈n⁴-Me(CH ₂₎₅C₂-2-C₄H₂S-5-C≡C-2-C ₄H₂S-5-C₂(CH₂₎₅Me} (32), as well as the homocoupling product [Mo₂Ir₂(CO)₈(n ⁵-C₅H₄Me)_2]2{u₈-n ⁴-Me(CH₂₎₅C₂-2-C₄H ₂S-5-C≡CC≡C-2-C₄H₂S5-C ₂(CH₂₎₅Me} (33). The identities of 21, 29, and 31 were confirmed by single-crystal X-ray diffraction studies. Cyclic voltammetric scans for these complexes all show a reversible/quasi-reversible oxidation followed by an irreversible oxidation process. Dicluster compounds linked by one heterocycle, and tricluster compounds, show two reduction processes, whereas dicluster compounds with longer bridges reveal only one reduction process.

Original language	English
Pages (from-to)	3659-3670
Number of pages	12
Journal	Organometallics
Volume	22
Issue number	18
DOIs	https://doi.org/10.1021/om030253b
Publication status	Published - 1 Sept 2003

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@article{de7f10042c6f449499a3928c973c32c7,

title = "Mixed-Metal Cluster Chemistry. 23. Synthesis and Crystallographic and Electrochemical Studies of Alkyne-Coordinated Group 6-Iridium Clusters Linked by Heterocyclic Groups",

abstract = "Reaction between the tetrahedral cluster compound Mo2Ir 2(CO)10(η5-C5H 4Me)2 (1) and 2-iodo-5-(oct-1′-ynyl)thiophene afforded the pseudooctahedral cluster Mo2Ir2\{U 4-n2Me(CH2)5C2-5-C4H 2S-2-I\}(CO)8(n5-C5H 4Me)2 (17) by formal insertion of the alkyne C≡C group into the Mo-Mo bond. Similar reactions of 1 or W2Ir 2(CO)10(n5-C5H4Me) 2 (2) with heterocyclic di- or triynes afforded the related mono-, di-, or tricluster compounds [M2lr2(CO)8(n 5-C5H4Me)2]2\{u8-n 4-Me(CH2)5C2-2-C4H 2-E-5-C2(CH2)5Me\} [E = S, M = Mo (20), W (21); E = Se, M = Mo (30), W (31)], [M2Ir2(CO) 8(n5-C5H4Me)2] 2\{u8n4-Me(CH2)5C 2-2-C4H2S-5-(E)-CH=CH-2C4H 2S-5-C2(CH2)5Me\} [M = Mo (22), W (24)], M 2Ir2\{u4-n2-Me(CH2)5C 2-2-C4-H2S-5-(E)-CH=CH-2-C4H 2S-5-C≡C(CH2)5Me\}(CO)8(n 5-C5H4Me)2 [M = Mo (23), W (25)], [M2Ir2(CO)8(n5C5H 4Me)2]3\{u12-n6-Me(CH 2)5C2-2-C4H2S-5-C 2-2-C4H2S-5-C2(CH2)5Me\} [M = Mo (26), W(28)], and[M2Ir2(CO)8(n 5-C5H4Me)2]2\{u8-n 4-Me(CH2)5C2-2-C4H 2S-5-C2-2-C4H2S-5-C≡C(CH 2)5Me\}[M = Mo (27), W (29)]. Compounds 27 and 29 correspond to the 1,2-dicluster adducts of the linear triyne Me(CH2)5C=C-5-C 4H2S-2-C≡C-2-C4H 2S-5-C≡C(CH2)5Me. No 1,3-dicluster isomer was isolated from direct reaction, but the molybdenum-containing 1,3-dicluster isomer was prepared by exploiting organic reaction chemistry on precoordinated functionalized alkyne ligands. Thus, Sonogashira coupling of 17 with trimethylsilylacetylene and subsequent desilylation gave Mo2Ir 2\{u4-n2-Me(CH2)5C 2-5-C4H2S-2-C≡CR\}(CO)8(n 5-C5H4Me)2 [R = SiMe3 (18), H (19)]. Sonogashira coupling of 17 and 19 gave the 1,3-isomer [Mo 2Ir2(CO)8(n5-C5H 4Me)2]2\{u8n4-Me(CH 2)5C2-2-C4H2S-5-C≡C-2-C 4H2S-5-C2(CH2)5Me\} (32), as well as the homocoupling product [Mo2Ir2(CO)8(n 5-C5H4Me)2]2\{u8-n 4-Me(CH2)5C2-2-C4H 2S-5-C≡CC≡C-2-C4H2S5-C 2(CH2)5Me\} (33). The identities of 21, 29, and 31 were confirmed by single-crystal X-ray diffraction studies. Cyclic voltammetric scans for these complexes all show a reversible/quasi-reversible oxidation followed by an irreversible oxidation process. Dicluster compounds linked by one heterocycle, and tricluster compounds, show two reduction processes, whereas dicluster compounds with longer bridges reveal only one reduction process.",

author = "Notaras, \{Eleni G.A.\} and Lucas, \{Nigel T.\} and Humphrey, \{Mark G.\} and Willis, \{Anthony C.\} and Rae, \{A. David\}",

year = "2003",

month = sep,

day = "1",

doi = "10.1021/om030253b",

language = "English",

volume = "22",

pages = "3659--3670",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "18",

}

TY - JOUR

T1 - Mixed-Metal Cluster Chemistry. 23. Synthesis and Crystallographic and Electrochemical Studies of Alkyne-Coordinated Group 6-Iridium Clusters Linked by Heterocyclic Groups

AU - Notaras, Eleni G.A.

AU - Lucas, Nigel T.

AU - Humphrey, Mark G.

AU - Willis, Anthony C.

AU - Rae, A. David

PY - 2003/9/1

Y1 - 2003/9/1

N2 - Reaction between the tetrahedral cluster compound Mo2Ir 2(CO)10(η5-C5H 4Me)2 (1) and 2-iodo-5-(oct-1′-ynyl)thiophene afforded the pseudooctahedral cluster Mo2Ir2{U 4-n2Me(CH2)5C2-5-C4H 2S-2-I}(CO)8(n5-C5H 4Me)2 (17) by formal insertion of the alkyne C≡C group into the Mo-Mo bond. Similar reactions of 1 or W2Ir 2(CO)10(n5-C5H4Me) 2 (2) with heterocyclic di- or triynes afforded the related mono-, di-, or tricluster compounds [M2lr2(CO)8(n 5-C5H4Me)2]2{u8-n 4-Me(CH2)5C2-2-C4H 2-E-5-C2(CH2)5Me} [E = S, M = Mo (20), W (21); E = Se, M = Mo (30), W (31)], [M2Ir2(CO) 8(n5-C5H4Me)2] 2{u8n4-Me(CH2)5C 2-2-C4H2S-5-(E)-CH=CH-2C4H 2S-5-C2(CH2)5Me} [M = Mo (22), W (24)], M 2Ir2{u4-n2-Me(CH2)5C 2-2-C4-H2S-5-(E)-CH=CH-2-C4H 2S-5-C≡C(CH2)5Me}(CO)8(n 5-C5H4Me)2 [M = Mo (23), W (25)], [M2Ir2(CO)8(n5C5H 4Me)2]3{u12-n6-Me(CH 2)5C2-2-C4H2S-5-C 2-2-C4H2S-5-C2(CH2)5Me} [M = Mo (26), W(28)], and[M2Ir2(CO)8(n 5-C5H4Me)2]2{u8-n 4-Me(CH2)5C2-2-C4H 2S-5-C2-2-C4H2S-5-C≡C(CH 2)5Me}[M = Mo (27), W (29)]. Compounds 27 and 29 correspond to the 1,2-dicluster adducts of the linear triyne Me(CH2)5C=C-5-C 4H2S-2-C≡C-2-C4H 2S-5-C≡C(CH2)5Me. No 1,3-dicluster isomer was isolated from direct reaction, but the molybdenum-containing 1,3-dicluster isomer was prepared by exploiting organic reaction chemistry on precoordinated functionalized alkyne ligands. Thus, Sonogashira coupling of 17 with trimethylsilylacetylene and subsequent desilylation gave Mo2Ir 2{u4-n2-Me(CH2)5C 2-5-C4H2S-2-C≡CR}(CO)8(n 5-C5H4Me)2 [R = SiMe3 (18), H (19)]. Sonogashira coupling of 17 and 19 gave the 1,3-isomer [Mo 2Ir2(CO)8(n5-C5H 4Me)2]2{u8n4-Me(CH 2)5C2-2-C4H2S-5-C≡C-2-C 4H2S-5-C2(CH2)5Me} (32), as well as the homocoupling product [Mo2Ir2(CO)8(n 5-C5H4Me)2]2{u8-n 4-Me(CH2)5C2-2-C4H 2S-5-C≡CC≡C-2-C4H2S5-C 2(CH2)5Me} (33). The identities of 21, 29, and 31 were confirmed by single-crystal X-ray diffraction studies. Cyclic voltammetric scans for these complexes all show a reversible/quasi-reversible oxidation followed by an irreversible oxidation process. Dicluster compounds linked by one heterocycle, and tricluster compounds, show two reduction processes, whereas dicluster compounds with longer bridges reveal only one reduction process.

AB - Reaction between the tetrahedral cluster compound Mo2Ir 2(CO)10(η5-C5H 4Me)2 (1) and 2-iodo-5-(oct-1′-ynyl)thiophene afforded the pseudooctahedral cluster Mo2Ir2{U 4-n2Me(CH2)5C2-5-C4H 2S-2-I}(CO)8(n5-C5H 4Me)2 (17) by formal insertion of the alkyne C≡C group into the Mo-Mo bond. Similar reactions of 1 or W2Ir 2(CO)10(n5-C5H4Me) 2 (2) with heterocyclic di- or triynes afforded the related mono-, di-, or tricluster compounds [M2lr2(CO)8(n 5-C5H4Me)2]2{u8-n 4-Me(CH2)5C2-2-C4H 2-E-5-C2(CH2)5Me} [E = S, M = Mo (20), W (21); E = Se, M = Mo (30), W (31)], [M2Ir2(CO) 8(n5-C5H4Me)2] 2{u8n4-Me(CH2)5C 2-2-C4H2S-5-(E)-CH=CH-2C4H 2S-5-C2(CH2)5Me} [M = Mo (22), W (24)], M 2Ir2{u4-n2-Me(CH2)5C 2-2-C4-H2S-5-(E)-CH=CH-2-C4H 2S-5-C≡C(CH2)5Me}(CO)8(n 5-C5H4Me)2 [M = Mo (23), W (25)], [M2Ir2(CO)8(n5C5H 4Me)2]3{u12-n6-Me(CH 2)5C2-2-C4H2S-5-C 2-2-C4H2S-5-C2(CH2)5Me} [M = Mo (26), W(28)], and[M2Ir2(CO)8(n 5-C5H4Me)2]2{u8-n 4-Me(CH2)5C2-2-C4H 2S-5-C2-2-C4H2S-5-C≡C(CH 2)5Me}[M = Mo (27), W (29)]. Compounds 27 and 29 correspond to the 1,2-dicluster adducts of the linear triyne Me(CH2)5C=C-5-C 4H2S-2-C≡C-2-C4H 2S-5-C≡C(CH2)5Me. No 1,3-dicluster isomer was isolated from direct reaction, but the molybdenum-containing 1,3-dicluster isomer was prepared by exploiting organic reaction chemistry on precoordinated functionalized alkyne ligands. Thus, Sonogashira coupling of 17 with trimethylsilylacetylene and subsequent desilylation gave Mo2Ir 2{u4-n2-Me(CH2)5C 2-5-C4H2S-2-C≡CR}(CO)8(n 5-C5H4Me)2 [R = SiMe3 (18), H (19)]. Sonogashira coupling of 17 and 19 gave the 1,3-isomer [Mo 2Ir2(CO)8(n5-C5H 4Me)2]2{u8n4-Me(CH 2)5C2-2-C4H2S-5-C≡C-2-C 4H2S-5-C2(CH2)5Me} (32), as well as the homocoupling product [Mo2Ir2(CO)8(n 5-C5H4Me)2]2{u8-n 4-Me(CH2)5C2-2-C4H 2S-5-C≡CC≡C-2-C4H2S5-C 2(CH2)5Me} (33). The identities of 21, 29, and 31 were confirmed by single-crystal X-ray diffraction studies. Cyclic voltammetric scans for these complexes all show a reversible/quasi-reversible oxidation followed by an irreversible oxidation process. Dicluster compounds linked by one heterocycle, and tricluster compounds, show two reduction processes, whereas dicluster compounds with longer bridges reveal only one reduction process.

UR - https://www.scopus.com/pages/publications/0041823197

U2 - 10.1021/om030253b

DO - 10.1021/om030253b

M3 - Article

SN - 0276-7333

VL - 22

SP - 3659

EP - 3670

JO - Organometallics

JF - Organometallics

IS - 18

ER -

Mixed-Metal Cluster Chemistry. 23. Synthesis and Crystallographic and Electrochemical Studies of Alkyne-Coordinated Group 6-Iridium Clusters Linked by Heterocyclic Groups

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