Synthesis, structure, spectroscopy, and reactivity of a metallathiabenzene

John R. Bleeke; Paul V. Hinkle; Nigam P. Rath

doi:10.1021/om010050s

Synthesis, structure, spectroscopy, and reactivity of a metallathiabenzene

John R. Bleeke
, Paul V. Hinkle
, Nigam P. Rath

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

65 Scopus citations

Abstract

Treatment of (Cl)Ir(PEt₃)₃ with lithium 2,3-dimethyl-5-thiapentadienide leads to the production of mer-CH=C(Me)C(Me)=CHSIr(PEt₃)₃(H) (4) via C-H bond activation. Oxidation of 4 with silver tetrafluoroborate in tetrahydrofuran generates "iridathiabenzene", [CH=C(Me)C(Me)=CHS=Ir(PEt₃)₃]⁺ BF₄^- (3). The structural and spectroscopic features of 3 are consistent with the presence of an aromatic ring in which the iridium center participates in ring π-bonding. Treatment of 3 with excess PMe₃ or with PPN⁺Cl^- leads to the production of CH=C(Me)C(Me)=CHSIr(PMe₃)₄⁺ BF₄^- (5) or mer-CH=C(Me)C(Me)=CHSIr(PEt₃)₃(Cl) (6), respectively. Each of these products features an iridathiacyclohexa-1,3-diene ring system. The reaction of 6 with 1/2 equiv of silver trifluoromethanesulfonate leads to the production of a novel iridium dimer, [(CH=C(Me)C(Me)=CHSIr(PEt₃)₂)₂ (μ-Cl)]⁺ O₃SCF₃^- (7), in which the two iridium centers are bridged by the two sulfur atoms of the iridathiacyclohexa-1,3-diene rings, as well as a chloride ligand. Treatment of 3 with nitrosobenzene generates a [4 + 2] cycloadduct, [CH=C(Me)C(Me)CH=SIrON(Ph)](PEt₃)₃⁺ BF₄^- (8), containing an iri-dathiacyclohexa-1,4-diene ring. Compound 3 cleanly displaces p-xylene from (η⁶-p-xylene)-Mo(CO)₃ in tetrahydrofuran, generating [η⁶-CH=C(Me)C(Me)=CHS=Ir(PEt₃)₃]Mo(CO)₃⁺ BF₄^- (9). When 9 is reacted with excess trimethylphosphine, PMe₃ adds to the molybdenum center, causing the iridathiabenzene ring to slip from η⁶ to η⁴ coordination and forming [η⁴-CH= C(Me)C(Me)=CHS=Ir(PEt₃)₂(CO)] Mo(PMe₃)₂(CO)₂⁺ BF₄^- (10). Finally, treatment of (η⁵-C₅-Me₅)Ru(NCMe)₃⁺ O₃SCF₃^- with 3 leads to clean displacement of the acetonitrile ligands by the iridathiabenzene ring and generation of the Ru sandwich compound [η⁶-CH=C(Me)C-(Me)=CHS=Ir(PEt₃)₃]Ru (η⁵-C₅Me₅)²⁺ BF₄^-O₃SCF₃^- (11). Compounds 3, 6a, 7, 9, and 10 have been structurally characterized by X-ray diffraction.

Original language	English
Pages (from-to)	1939-1951
Number of pages	13
Journal	Organometallics
Volume	20
Issue number	10
DOIs	https://doi.org/10.1021/om010050s
State	Published - May 14 2001

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@article{ce0591c9b2a94fe685670e381210620d,

title = "Synthesis, structure, spectroscopy, and reactivity of a metallathiabenzene",

abstract = "Treatment of (Cl)Ir(PEt3)3 with lithium 2,3-dimethyl-5-thiapentadienide leads to the production of mer-CH=C(Me)C(Me)=CHSIr(PEt3)3(H) (4) via C-H bond activation. Oxidation of 4 with silver tetrafluoroborate in tetrahydrofuran generates {"}iridathiabenzene{"}, [CH=C(Me)C(Me)=CHS=Ir(PEt3)3]+ BF4- (3). The structural and spectroscopic features of 3 are consistent with the presence of an aromatic ring in which the iridium center participates in ring π-bonding. Treatment of 3 with excess PMe3 or with PPN+Cl- leads to the production of CH=C(Me)C(Me)=CHSIr(PMe3)4+ BF4- (5) or mer-CH=C(Me)C(Me)=CHSIr(PEt3)3(Cl) (6), respectively. Each of these products features an iridathiacyclohexa-1,3-diene ring system. The reaction of 6 with 1/2 equiv of silver trifluoromethanesulfonate leads to the production of a novel iridium dimer, [(CH=C(Me)C(Me)=CHSIr(PEt3)2)2 (μ-Cl)]+ O3SCF3- (7), in which the two iridium centers are bridged by the two sulfur atoms of the iridathiacyclohexa-1,3-diene rings, as well as a chloride ligand. Treatment of 3 with nitrosobenzene generates a [4 + 2] cycloadduct, [CH=C(Me)C(Me)CH=SIrON(Ph)](PEt3)3+ BF4- (8), containing an iri-dathiacyclohexa-1,4-diene ring. Compound 3 cleanly displaces p-xylene from (η6-p-xylene)-Mo(CO)3 in tetrahydrofuran, generating [η6-CH=C(Me)C(Me)=CHS=Ir(PEt3)3]Mo(CO) 3+ BF4- (9). When 9 is reacted with excess trimethylphosphine, PMe3 adds to the molybdenum center, causing the iridathiabenzene ring to slip from η6 to η4 coordination and forming [η4-CH= C(Me)C(Me)=CHS=Ir(PEt3)2(CO)] Mo(PMe3)2(CO)2+ BF4- (10). Finally, treatment of (η5-C5-Me5)Ru(NCMe)3+ O3SCF3- with 3 leads to clean displacement of the acetonitrile ligands by the iridathiabenzene ring and generation of the Ru sandwich compound [η6-CH=C(Me)C-(Me)=CHS=Ir(PEt3)3]Ru (η5-C5Me5)2+ BF4-O3SCF3- (11). Compounds 3, 6a, 7, 9, and 10 have been structurally characterized by X-ray diffraction.",

author = "Bleeke, \{John R.\} and Hinkle, \{Paul V.\} and Rath, \{Nigam P.\}",

year = "2001",

month = may,

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doi = "10.1021/om010050s",

language = "English",

volume = "20",

pages = "1939--1951",

journal = "Organometallics",

issn = "0276-7333",

number = "10",

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TY - JOUR

T1 - Synthesis, structure, spectroscopy, and reactivity of a metallathiabenzene

AU - Bleeke, John R.

AU - Hinkle, Paul V.

AU - Rath, Nigam P.

PY - 2001/5/14

Y1 - 2001/5/14

N2 - Treatment of (Cl)Ir(PEt3)3 with lithium 2,3-dimethyl-5-thiapentadienide leads to the production of mer-CH=C(Me)C(Me)=CHSIr(PEt3)3(H) (4) via C-H bond activation. Oxidation of 4 with silver tetrafluoroborate in tetrahydrofuran generates "iridathiabenzene", [CH=C(Me)C(Me)=CHS=Ir(PEt3)3]+ BF4- (3). The structural and spectroscopic features of 3 are consistent with the presence of an aromatic ring in which the iridium center participates in ring π-bonding. Treatment of 3 with excess PMe3 or with PPN+Cl- leads to the production of CH=C(Me)C(Me)=CHSIr(PMe3)4+ BF4- (5) or mer-CH=C(Me)C(Me)=CHSIr(PEt3)3(Cl) (6), respectively. Each of these products features an iridathiacyclohexa-1,3-diene ring system. The reaction of 6 with 1/2 equiv of silver trifluoromethanesulfonate leads to the production of a novel iridium dimer, [(CH=C(Me)C(Me)=CHSIr(PEt3)2)2 (μ-Cl)]+ O3SCF3- (7), in which the two iridium centers are bridged by the two sulfur atoms of the iridathiacyclohexa-1,3-diene rings, as well as a chloride ligand. Treatment of 3 with nitrosobenzene generates a [4 + 2] cycloadduct, [CH=C(Me)C(Me)CH=SIrON(Ph)](PEt3)3+ BF4- (8), containing an iri-dathiacyclohexa-1,4-diene ring. Compound 3 cleanly displaces p-xylene from (η6-p-xylene)-Mo(CO)3 in tetrahydrofuran, generating [η6-CH=C(Me)C(Me)=CHS=Ir(PEt3)3]Mo(CO) 3+ BF4- (9). When 9 is reacted with excess trimethylphosphine, PMe3 adds to the molybdenum center, causing the iridathiabenzene ring to slip from η6 to η4 coordination and forming [η4-CH= C(Me)C(Me)=CHS=Ir(PEt3)2(CO)] Mo(PMe3)2(CO)2+ BF4- (10). Finally, treatment of (η5-C5-Me5)Ru(NCMe)3+ O3SCF3- with 3 leads to clean displacement of the acetonitrile ligands by the iridathiabenzene ring and generation of the Ru sandwich compound [η6-CH=C(Me)C-(Me)=CHS=Ir(PEt3)3]Ru (η5-C5Me5)2+ BF4-O3SCF3- (11). Compounds 3, 6a, 7, 9, and 10 have been structurally characterized by X-ray diffraction.

AB - Treatment of (Cl)Ir(PEt3)3 with lithium 2,3-dimethyl-5-thiapentadienide leads to the production of mer-CH=C(Me)C(Me)=CHSIr(PEt3)3(H) (4) via C-H bond activation. Oxidation of 4 with silver tetrafluoroborate in tetrahydrofuran generates "iridathiabenzene", [CH=C(Me)C(Me)=CHS=Ir(PEt3)3]+ BF4- (3). The structural and spectroscopic features of 3 are consistent with the presence of an aromatic ring in which the iridium center participates in ring π-bonding. Treatment of 3 with excess PMe3 or with PPN+Cl- leads to the production of CH=C(Me)C(Me)=CHSIr(PMe3)4+ BF4- (5) or mer-CH=C(Me)C(Me)=CHSIr(PEt3)3(Cl) (6), respectively. Each of these products features an iridathiacyclohexa-1,3-diene ring system. The reaction of 6 with 1/2 equiv of silver trifluoromethanesulfonate leads to the production of a novel iridium dimer, [(CH=C(Me)C(Me)=CHSIr(PEt3)2)2 (μ-Cl)]+ O3SCF3- (7), in which the two iridium centers are bridged by the two sulfur atoms of the iridathiacyclohexa-1,3-diene rings, as well as a chloride ligand. Treatment of 3 with nitrosobenzene generates a [4 + 2] cycloadduct, [CH=C(Me)C(Me)CH=SIrON(Ph)](PEt3)3+ BF4- (8), containing an iri-dathiacyclohexa-1,4-diene ring. Compound 3 cleanly displaces p-xylene from (η6-p-xylene)-Mo(CO)3 in tetrahydrofuran, generating [η6-CH=C(Me)C(Me)=CHS=Ir(PEt3)3]Mo(CO) 3+ BF4- (9). When 9 is reacted with excess trimethylphosphine, PMe3 adds to the molybdenum center, causing the iridathiabenzene ring to slip from η6 to η4 coordination and forming [η4-CH= C(Me)C(Me)=CHS=Ir(PEt3)2(CO)] Mo(PMe3)2(CO)2+ BF4- (10). Finally, treatment of (η5-C5-Me5)Ru(NCMe)3+ O3SCF3- with 3 leads to clean displacement of the acetonitrile ligands by the iridathiabenzene ring and generation of the Ru sandwich compound [η6-CH=C(Me)C-(Me)=CHS=Ir(PEt3)3]Ru (η5-C5Me5)2+ BF4-O3SCF3- (11). Compounds 3, 6a, 7, 9, and 10 have been structurally characterized by X-ray diffraction.

UR - https://www.scopus.com/pages/publications/0035858948

U2 - 10.1021/om010050s

DO - 10.1021/om010050s

M3 - Article

AN - SCOPUS:0035858948

SN - 0276-7333

VL - 20

SP - 1939

EP - 1951

JO - Organometallics

JF - Organometallics

IS - 10

ER -

Synthesis, structure, spectroscopy, and reactivity of a metallathiabenzene

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