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Substitution at rhodium and iridium centres with a bulky phosphine; trans-[M(P(4-biphenyl)3)2(CO)Cl] (M = Rh, Ir)

SyntheticPage 810
DOI: 10.1039/SP810
Submitted Sep 02, 2016, published Sep 02, 2016
Thibault Troadec (t.troadec@warwick.ac.uk), Richard Knighton (r.c.knighton@warwick.ac.uk), Adrian Chaplin (a.b.chaplin@warwick.ac.uk)
A contribution from Chaplin group, University of Warwick


			Reaction Scheme: Substitution at rhodium and iridium centres with a bulky phosphine

Chemicals Used

Dichloromethane
Pentane
[Rh(CO)2Cl]2  (ref 1)
[Ir(COD)Cl]2 (ref 2)
P(4-biphenyl)3 (ref 3)

Procedure

trans-[Rh(P(4-biphenyl)3)2(CO)Cl] (1): A J. Young’s Flask was charged with [Rh(CO)2Cl]2 (30 mg, 0.077 mmol) and P(4-biphenyl)3 (151 mg, 0.309 mmol), and CH2Cl2 (4 mL) added at room temperature. The reaction mixture was stirred for 5 minutes and the solvent removed in vacuo. The resulting yellow powder was washed with pentane (2 x 3 mL), to afford the pure product as yellow solid (Yield = 168 mg, 95%). Crystals suitable for X-Ray diffraction analysis were grown by slow diffusion of pentane into a CH2Cl2 solution.

trans-[Ir(P(4-biphenyl)3)2(CO)Cl] (2): A J. Young’s Flask was charged with [Ir(COD)2Cl]2 (150 mg, 0.223 mmol) and P(4-biphenyl)3 (438 mg, 0.892 mmol), and CH2Cl2 (4 mL) added. The reaction mixture was freeze-pump-thaw degassed, placed under an atmosphere of CO and stirred for 5 minutes. The solvent removed in vacuo and the resulting yellow powder was washed with pentane (2 x 3 mL). Crystals suitable for X-Ray diffraction analysis were grown by slow diffusion of pentane into a CH2Cl2 solution (Yield = 453 mg, 82%).

Author's Comments

All manipulations were performed under an atmosphere of nitrogen, using Schlenk and glove box techniques. Glassware was oven dried at 150ºC overnight and flamed under vacuum prior to use. Anhydrous CH2Cl2 and pentane were purchased and handled strictly under an inert atmosphere. CD2Cl2 was dried over CaH2, vacuum distilled, and freeze-pump-thaw degassed three times before being placed under argon. Microanalyses were performed by Stephen Boyer at London Metropolitan University. Extreme caution is advised when using carbon monoxide gas: all manipulations and venting of CO should be carried within an efficient fumehood. Use of a personal gas detector is strongly advised.

Data

[Rh(P(4-biphenyl)3)2(CO)Cl] (1)

1H NMR (600 MHz, CD2Cl2) δ 7.90-7.95 (m, 12H), 7.72 (d, JHH = 8.0, 12H), 7.67 (d, JHH = 7.3, 12H), 7.47 (t, JHH = 7.3, 12H), 7.39 (t, JHH = 7.3, 6H). 13C{1H} NMR (151 MHz, CD2Cl2) δ 187.4 (dt, JRhC = 75, JPC = 16) 143.5 (s), 140.6 (s), 135.7 (t, JPC = 7), 132.3 (t, JPC = 23), 129.4 (s), 128.5 (s), 127.7 (s), 127.4 (t, JPC = 5). 31P{1H} NMR (243 MHz, CD2Cl2) δ 27.8 (JRhP = 126). Anal. Calcd for C73H54ClOP2Rh (1147.51 gmol-1): C, 76.41; H, 4.74. Found: C, 76.37; H, 4.82. IR (CH2Cl2, cm-1): ν(CO) 1978. The solid-state structure of this compound has been deposited with the Cambridge Crystallographic Data Centre under CCDC 1498191

 [Ir(P(4-biphenyl)3)2(CO)Cl] (2)

1H NMR (400 MHz, CD2Cl2) δ 7.94 (br d, JHH = 7.8, 12H), 7.67-7.82 (m, 24H), 7.37-7.55 (m, 18H). 13C{1H} NMR (101 MHz, CD2Cl2) δ 172.2 (t, JPC = 11), 143.7 (s), 140.5 (s), 135.9 (t, JPC = 6), 131.6 (t, JPC = 27), 129.5 (s), 128.5 (s), 127.8 (s), 127.4 (t, JPC = 5). 31P{1H} NMR (122 MHz, CD2Cl2) δ 22.8. Anal. Calcd for C73H54ClOP2Ir (1236.82 gmol-1): C, 70.89; H, 4.40. Found: C, 71.01; H, 4.60. IR (CH2Cl2, cm-1): ν(CO) 1965. The solid-state structure of this compound has been deposited with the Cambridge Crystallographic Data Centre under CCDC 1498192.


Lead Reference

 

Other References

1. J. A. McCleverty, G. Wilkinson, L. G. Lipson, M. L. Maddox, H. D. Kaesz, Inorg. Synth. 1990, 28, 84–86.
http://dx.doi.org/10.1002/9780470132593.ch20
2. J. L. Herde, J. C. Lambert, C. V. Senoff, M. A. Cushing, Inorg. Synth. 1974, 15, 18–20.
http://dx.doi.org/10.1002/9780470132463.ch5
3. M. Joshaghani, E. Faramarzi, E. Rafiee, M. Daryanavard, J. Xiao, C. Baillie, J. Mol. Catal. A: Chem. 2006, 259, 35–40.
http://dx.doi.org/10.1016/j.molcata.2006.05.062

Supplementary Information

 

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Keywords: carbonyl, chloride, iridium, organometallics, phosphine, rhodium

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