Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters Dedicated to Professor Jack Lewis, a cluster chemist par excellence.

Junhong Fu; Graeme J. Moxey; Mahbod Morshedi; Adam Barlow; Michael D. Randles; Peter V. Simpson; Torsten Schwich; Marie P. Cifuentes; Mark G. Humphrey

doi:10.1016/j.jorganchem.2015.09.034

Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters Dedicated to Professor Jack Lewis, a cluster chemist par excellence.

Junhong Fu, Graeme J. Moxey, Mahbod Morshedi, Adam Barlow, Michael D. Randles, Peter V. Simpson, Torsten Schwich, Marie P. Cifuentes, Mark G. Humphrey^*

^*Corresponding author for this work

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

5 Citations (Scopus)

Abstract

Tetrahedral Mo₂Ir₂(μ₃-CO)(μ-CO)₅(CO)₄(η⁵-C₅H₅)₂ (1) reacted with P(C₆H₄Me-4)₃, P(C₆H₂Me₂-3,5-OMe-4)₃, and AsPh₃ to afford the substitution products Mo₂Ir₂(μ-CO)₃(CO)₆(L)(η⁵-C₅H₅)₂ [L = P(C₆H₄Me-4)₃ (3), P(C₆H₂Me₂-3,5-OMe-4)₃ (4), AsPh₃ (5)] in fair to good yields, while reaction of 1 with HC≡CSiPrⁱ₃ proceeded by insertion into the Mo-Mo bond to give the pseudo-octahedral Mo₂Ir₂(μ₄-η²-HC₂SiPrⁱ₃)(μ-CO)₄(CO)₄(η⁵-C₅H₅)₂ (6) in fair yield. While MoIr₃(μ-CO)₃(CO)₇(η⁵-C₅H₅) reacted with HC≡CSiMe₃ to give a complex mixture of thus-far-uncharacterized products, its phosphine substitution product MoIr₃(μ-CO)₃(CO)₅(PPh₃)₂(η⁵-C₅H₅) reacted with the same alkyne via insertion into a Mo-Ir bond to afford the pseudo-octahedral MoIr₃(μ₄-η²-HC₂SiMe₃)(μ-CO)₃(CO)₄(PPh₃)₂(η⁵-C₅H₅) (8) in good yield. Clusters 4, 5 (two isomers), 6 and 8 have been characterized by single-crystal X-ray diffraction studies. Cyclic voltammetric studies of Mo₂Ir₂(μ-CO)₃(CO)₆(PPh₃)(η⁵-C₅H₅)₂ (2), 3-6 and 8 confirmed the tuning of redox potentials upon phosphines/arsine introduction and alkyne modification. IR spectroelectrochemical studies of 2, 6, and 8 suggest decreasing proclivity for bridging carbonyl ligands following oxidation. Variable temperature ³¹P NMR studies of 3 and 4 revealed interconverting isomers in solution, the structures of which are assigned as analogues of the X-ray diffraction-confirmed isomers of 5. Studies of 2-5 using ns pulses and the open-aperture Z-scan technique revealed that all are optical limiters at wavelengths in the visible region.

Original language	English
Pages (from-to)	135-144
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	812
DOIs	https://doi.org/10.1016/j.jorganchem.2015.09.034
Publication status	Published - 15 Jun 2016

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Fu, J., Moxey, G. J., Morshedi, M., Barlow, A., Randles, M. D., Simpson, P. V., Schwich, T., Cifuentes, M. P., & Humphrey, M. G. (2016). Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters Dedicated to Professor Jack Lewis, a cluster chemist par excellence. Journal of Organometallic Chemistry, 812, 135-144. https://doi.org/10.1016/j.jorganchem.2015.09.034

@article{e226bf0068714167912e96e3dbfbf30b,

title = "Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters Dedicated to Professor Jack Lewis, a cluster chemist par excellence.",

abstract = "Tetrahedral Mo2Ir2(μ3-CO)(μ-CO)5(CO)4(η5-C5H5)2 (1) reacted with P(C6H4Me-4)3, P(C6H2Me2-3,5-OMe-4)3, and AsPh3 to afford the substitution products Mo2Ir2(μ-CO)3(CO)6(L)(η5-C5H5)2 [L = P(C6H4Me-4)3 (3), P(C6H2Me2-3,5-OMe-4)3 (4), AsPh3 (5)] in fair to good yields, while reaction of 1 with HC≡CSiPri3 proceeded by insertion into the Mo-Mo bond to give the pseudo-octahedral Mo2Ir2(μ4-η2-HC2SiPri3)(μ-CO)4(CO)4(η5-C5H5)2 (6) in fair yield. While MoIr3(μ-CO)3(CO)7(η5-C5H5) reacted with HC≡CSiMe3 to give a complex mixture of thus-far-uncharacterized products, its phosphine substitution product MoIr3(μ-CO)3(CO)5(PPh3)2(η5-C5H5) reacted with the same alkyne via insertion into a Mo-Ir bond to afford the pseudo-octahedral MoIr3(μ4-η2-HC2SiMe3)(μ-CO)3(CO)4(PPh3)2(η5-C5H5) (8) in good yield. Clusters 4, 5 (two isomers), 6 and 8 have been characterized by single-crystal X-ray diffraction studies. Cyclic voltammetric studies of Mo2Ir2(μ-CO)3(CO)6(PPh3)(η5-C5H5)2 (2), 3-6 and 8 confirmed the tuning of redox potentials upon phosphines/arsine introduction and alkyne modification. IR spectroelectrochemical studies of 2, 6, and 8 suggest decreasing proclivity for bridging carbonyl ligands following oxidation. Variable temperature 31P NMR studies of 3 and 4 revealed interconverting isomers in solution, the structures of which are assigned as analogues of the X-ray diffraction-confirmed isomers of 5. Studies of 2-5 using ns pulses and the open-aperture Z-scan technique revealed that all are optical limiters at wavelengths in the visible region.",

keywords = "Cluster, Crystal structures, Cyclopentadienyl, Iridium, Molybdenum",

author = "Junhong Fu and Moxey, {Graeme J.} and Mahbod Morshedi and Adam Barlow and Randles, {Michael D.} and Simpson, {Peter V.} and Torsten Schwich and Cifuentes, {Marie P.} and Humphrey, {Mark G.}",

year = "2016",

month = jun,

day = "15",

doi = "10.1016/j.jorganchem.2015.09.034",

language = "English",

volume = "812",

pages = "135--144",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

}

Fu, J, Moxey, GJ, Morshedi, M, Barlow, A, Randles, MD, Simpson, PV, Schwich, T, Cifuentes, MP & Humphrey, MG 2016, 'Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters Dedicated to Professor Jack Lewis, a cluster chemist par excellence.', Journal of Organometallic Chemistry, vol. 812, pp. 135-144. https://doi.org/10.1016/j.jorganchem.2015.09.034

Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters Dedicated to Professor Jack Lewis, a cluster chemist par excellence. / Fu, Junhong; Moxey, Graeme J.; Morshedi, Mahbod et al.
In: Journal of Organometallic Chemistry, Vol. 812, 15.06.2016, p. 135-144.

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

TY - JOUR

T1 - Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters Dedicated to Professor Jack Lewis, a cluster chemist par excellence.

AU - Fu, Junhong

AU - Moxey, Graeme J.

AU - Morshedi, Mahbod

AU - Barlow, Adam

AU - Randles, Michael D.

AU - Simpson, Peter V.

AU - Schwich, Torsten

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

PY - 2016/6/15

Y1 - 2016/6/15

N2 - Tetrahedral Mo2Ir2(μ3-CO)(μ-CO)5(CO)4(η5-C5H5)2 (1) reacted with P(C6H4Me-4)3, P(C6H2Me2-3,5-OMe-4)3, and AsPh3 to afford the substitution products Mo2Ir2(μ-CO)3(CO)6(L)(η5-C5H5)2 [L = P(C6H4Me-4)3 (3), P(C6H2Me2-3,5-OMe-4)3 (4), AsPh3 (5)] in fair to good yields, while reaction of 1 with HC≡CSiPri3 proceeded by insertion into the Mo-Mo bond to give the pseudo-octahedral Mo2Ir2(μ4-η2-HC2SiPri3)(μ-CO)4(CO)4(η5-C5H5)2 (6) in fair yield. While MoIr3(μ-CO)3(CO)7(η5-C5H5) reacted with HC≡CSiMe3 to give a complex mixture of thus-far-uncharacterized products, its phosphine substitution product MoIr3(μ-CO)3(CO)5(PPh3)2(η5-C5H5) reacted with the same alkyne via insertion into a Mo-Ir bond to afford the pseudo-octahedral MoIr3(μ4-η2-HC2SiMe3)(μ-CO)3(CO)4(PPh3)2(η5-C5H5) (8) in good yield. Clusters 4, 5 (two isomers), 6 and 8 have been characterized by single-crystal X-ray diffraction studies. Cyclic voltammetric studies of Mo2Ir2(μ-CO)3(CO)6(PPh3)(η5-C5H5)2 (2), 3-6 and 8 confirmed the tuning of redox potentials upon phosphines/arsine introduction and alkyne modification. IR spectroelectrochemical studies of 2, 6, and 8 suggest decreasing proclivity for bridging carbonyl ligands following oxidation. Variable temperature 31P NMR studies of 3 and 4 revealed interconverting isomers in solution, the structures of which are assigned as analogues of the X-ray diffraction-confirmed isomers of 5. Studies of 2-5 using ns pulses and the open-aperture Z-scan technique revealed that all are optical limiters at wavelengths in the visible region.

AB - Tetrahedral Mo2Ir2(μ3-CO)(μ-CO)5(CO)4(η5-C5H5)2 (1) reacted with P(C6H4Me-4)3, P(C6H2Me2-3,5-OMe-4)3, and AsPh3 to afford the substitution products Mo2Ir2(μ-CO)3(CO)6(L)(η5-C5H5)2 [L = P(C6H4Me-4)3 (3), P(C6H2Me2-3,5-OMe-4)3 (4), AsPh3 (5)] in fair to good yields, while reaction of 1 with HC≡CSiPri3 proceeded by insertion into the Mo-Mo bond to give the pseudo-octahedral Mo2Ir2(μ4-η2-HC2SiPri3)(μ-CO)4(CO)4(η5-C5H5)2 (6) in fair yield. While MoIr3(μ-CO)3(CO)7(η5-C5H5) reacted with HC≡CSiMe3 to give a complex mixture of thus-far-uncharacterized products, its phosphine substitution product MoIr3(μ-CO)3(CO)5(PPh3)2(η5-C5H5) reacted with the same alkyne via insertion into a Mo-Ir bond to afford the pseudo-octahedral MoIr3(μ4-η2-HC2SiMe3)(μ-CO)3(CO)4(PPh3)2(η5-C5H5) (8) in good yield. Clusters 4, 5 (two isomers), 6 and 8 have been characterized by single-crystal X-ray diffraction studies. Cyclic voltammetric studies of Mo2Ir2(μ-CO)3(CO)6(PPh3)(η5-C5H5)2 (2), 3-6 and 8 confirmed the tuning of redox potentials upon phosphines/arsine introduction and alkyne modification. IR spectroelectrochemical studies of 2, 6, and 8 suggest decreasing proclivity for bridging carbonyl ligands following oxidation. Variable temperature 31P NMR studies of 3 and 4 revealed interconverting isomers in solution, the structures of which are assigned as analogues of the X-ray diffraction-confirmed isomers of 5. Studies of 2-5 using ns pulses and the open-aperture Z-scan technique revealed that all are optical limiters at wavelengths in the visible region.

KW - Cluster

KW - Crystal structures

KW - Cyclopentadienyl

KW - Iridium

KW - Molybdenum

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U2 - 10.1016/j.jorganchem.2015.09.034

DO - 10.1016/j.jorganchem.2015.09.034

M3 - Article

SN - 0022-328X

VL - 812

SP - 135

EP - 144

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Fu J, Moxey GJ, Morshedi M, Barlow A, Randles MD, Simpson PV et al. Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters Dedicated to Professor Jack Lewis, a cluster chemist par excellence. Journal of Organometallic Chemistry. 2016 Jun 15;812:135-144. doi: 10.1016/j.jorganchem.2015.09.034

Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters Dedicated to Professor Jack Lewis, a cluster chemist par excellence.

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