1,5,9-Triphosphacyclododecane complexes of molybdenum and tungsten; crystal structure of tricarbonyl[1,5,9-tris(isopropyl)-1,5,9-triphosphacyclododecane]-molybdenum(0)

Spectroscopic and Electrochemical Studies of Group 6 and 8 Transition Metal Carbonyl Derivatives of tris{(diphenylphosphinomethyl)dimethylsilyl}methane

“…[19][20][21][22][23] The pattern is characteristic of a complex in which the [M(CO) 3 ] moiety is attached to a triphosphine ligand. [3,7,24] The ν(CO) bands are similar to those reported for related compounds, [M(CO) 3 {(Ph 2 PMe 2 Si) 3 CH}] (M = Cr, W), [9] [{(Ph 2 PCH 2 CH 2 ) 2 PPh}M(CO) 3 ] (M = Cr, [25] W [24] ), [CH(CH 2 PPh 2 ) 2 ] 2 Cr(CO) 3 , [26] [W(CO) 3 {cyclo-(Me 3 SiCH 2 PC 3 H 6 ) 3 }], [27] [{CH(Ph 2 P) 2 CH 2 PPh 2 }W(CO) 3 ], [8,28] [W(CO) 3 L 3 ] (L 3 = MeC(CH 2 SMe) 3 ), [29] and [Fe(CO) 3 (TPM)] (TPM = tris(diphenylphosphino)methane. [7] Electronic Spectra…”

Template synthesis of 9-membered triphospha-macrocycles with rigid o-phenylene backbone functions

“…Alkylation of the co-ordinated secondary phosphines in 12membered P 3 -macrocycles has previously been achieved by hydrophosphination with alkenes. 6 We have also reported selective functionalisation of these ligands by base deprotonation of the co-ordinated secondary phosphines followed by nucleophilic substitution of halide in an appropriate alkyl halide electrophile. 7 This method is also established for iron secondary phosphine complexes.…”

“…6d was isolated as orange needles from a cooled solution of EtOH in 79% yield 1. H NMR d ppm: 1.8 (br m, 2H, CH 2 ), 1.1-1.2 (br m, 2H, CH 2 ), 1.17 (m, 3H, PCH 2 CH 3 ), 1.71 (s, 15H, CpCH 3 ), 1.7-2.1 (br m, 4H, CH 2 ), 2.01 (m, 2H, PCH 2 CH 3 ), 3.89 (s, 3H, PhOCH 3 ), 6.09 (d m, 1H, PH, 1 J P-H = 351 Hz),6.24 (d m, 1H, PH, 1 J P-H = 363 Hz), 6.86 (br m, 1H, Ph), 7.24 (br m, 1H, Ph), 7.46 (br m, 1H, Ph) 13. C NMR d ppm: 9.3 (PCH 2 CH 3 ), 11.2 (CpCH 3 ), 20.5 (m, PCH 2 CH 3 ), 23.2 (m, CH 2 ), 25.1 (m, CH 2 ), 25.9 (m, CH 2 ), 56.4 (PhOCH 3 ), 89.2 (Cp), 112.7 (Ph), 122.8 (Ph), 135.3 (Ph), 144.7 (Ph), 151.5 (Ph), 158.6 (Ph).…”

“…The orange needle crystals formed were isolated by filtration (0.23 mmol, 76.7%). 1 H NMR d ppm: 0.05 (m, 1H, CH 2 ), 0.4 (m, 1H, CH 2 ), 0.66 (m, 3H, PCH 2 CH 3 ), 0.79 (m, 3H, PCH 2 CH 3 ), 1.11 (m, 3H, PCH 2 CH 3 ), 1.70 (s, 15H, CpCH 3 ), 1.7-1.9 (br m, 4H, CH 2 ), 1.95 (m, 2H, PCH 2 CH 3 ), 2.24 (m, 2H, PCH 2 CH 3 ), 2.3-2.5 (br m, 2H, CH 2 ), 2.84 (m, 2H, PCH 2 CH 3 ), 3.77 (s, 3H, PhOCH 3 ), 6.73 (br m, 1H, Ph), 6.95 (br m, 1H, Ph), 7.37 (br m, 1H, Ph). 13 The solution was allowed to slowly warm to room temperature while stirring.…”

Chromium and molybdenum complexes of tertiary alkyl and pendant donor triphosphamacrocycles

“…Compounds of this nature have been shown to be of value in this field and it has been suggested that the relatively enhanced lability of the 'hard' donor may well improve the availability of vacant coordination sites in solution whilst the chelate effect maintains their potential ability to stabilise catalytically active species. 4 During our investigation of routes to free triphosphorus macrocycles we have recently reported the formation of the first tritertiary complexes of 1,5,9-triphosphacyclododecane with molybdenum and tungsten, 5 and the oxidation of these compounds with halogens. 6 In order to improve our understanding of the behaviour of these ligand systems as well as to further investigate efficient preparative routes, we have expanded our study to chromium including the high-yield synthesis and structural characterisation of the first chromium trisecondary 1,5,9triphosphacyclododecane complex, tricarbonyl(1,5,9-triphosphacyclododecane)chromium(0) 1.…”