31P NMR studies of cis-[RhCl(CO)(bis-phosphine)] complexes

Dyer, G.; Wharf, Rosalind M.; Hill, W. E.

doi:10.1016/s0020-1693(00)84385-6

Cited by 14 publications

(11 citation statements)

References 20 publications

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“…Additionally, this nucleus experiences a smaller deshielding. These observations agree well with similar rhodium(I) complexes , and are caused by the trans effect of the CO ligand. The 2 J PP coupling constants provide additional stereochemical information.…”

Section: Results and Discussionsupporting

confidence: 91%

“…However, its presence is evident from IR spectroscopy, which shows an intense band for the CO stretching vibration at 2007 cm –1 . This value is very similar to cis -coordinated complexes of bis-phosphines. , For instance, the CO stretching vibration of the bis(diphenylphosphino)ethane (dppe) complex [RhCl(dppe)(CO)] is observed at 2010 cm –1 . Therefore, the electronic properties of octaphosphine ligand 1 are comparable to classical bis-phosphines.…”

Section: Results and Discussionsupporting

confidence: 67%

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Versatile Coordination Chemistry of Hexa-tert-butyl-octaphosphine

Grell

Hey‐Hawkins

2020

Inorg. Chem.

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The octaphosphine {cyclo-(P 4 t Bu 3 )} 2 (1) possesses a multifaceted coordination chemistry. The predominant binding mode is a P,P-chelate, e.g., in the monometallic chelate complex [MLL′(1κ 2 P 2 ,P 4 ′)] in which the ligand 1 adopts a gauche conformation. Examples include square-planar (M = Rh I , L = CO, L′ = Cl (2), M = Pd II , L = L′ = Cl (3), M = Pt II , L = L′ = Cl (9)), tetrahedral (M = Co −I , L = NO, L′ = CO (4)), and trigonal-planar complexes [ML(1-κ 2 P 2 ,P 4 ′)] (M = Pd 0 , L = PPh 3 , (5), M = Cu I , L = Br (6)). With 2 equiv of [CuBr(SMe 2 )], a dinuclear complex [(CuBr) 2 (1-κ 2 P 2 ,P 2 ′,κ 2 P 4 ,P 4 ′)] (7) was obtained which features a synperiplanar conformation of the octaphosphine. A second coordination mode was also observed in [PtCl 2 (1-κ 2 P 1 ,P 2 ′)] (10) in which the bridge phosphorus atom in octaphosphine 1 is involved in the chelation, with the ligand in an antiperiplanar conformation. Thermolysis of selected complexes showed them to be suitable candidates for the generation of phosphorus-rich metal phosphides MP x (x > 1).

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Section: Results and Discussionsupporting

confidence: 91%

Section: Results and Discussionsupporting

confidence: 67%

Versatile Coordination Chemistry of Hexa-tert-butyl-octaphosphine

Grell

Hey‐Hawkins

2020

Inorg. Chem.

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“…50% yield. However, in the presence of a 2-fold excess of BINAP, under a CO/O 2 (1:1) gas mixture, 3 is formed quantitatively, as observed by monitoring the intensity of the infrared S1), solution FTIR analysis of the ν CO stretching frequencies (Table 1), solution 31 P{ 1 H} NMR (Table 2), and mass spectrometry. The purity of the compounds was demonstrated by the sharpness of the bands in the NMR spectra and the absence of any that were attributable to possible significant impurities (Figures S1-S3).…”

Section: Resultsmentioning

confidence: 96%

“…Phosphorus NMR Spectroscopy. The solution 31 P-{ 1 H} NMR spectrum in C 6 D 6 of 1 exhibits a single doublet at 50 ppm (J RhP ) 195 Hz). The 31 P{ 1 H} NMR spectrum of 2 in CD 6 D 6 consists of a doublet of doublets at 46.5 and 26.0 ppm (J Rh-P ) 162 and 128 Hz, J P-P ) 44 Hz), and 3 exhibits a doublet at 49.2 ppm (J Rh-P ) 175 Hz) and a singlet at 41.9 ppm.…”

Section: Resultsmentioning

confidence: 99%

“…( ligands prefer a bridging orientation rather than an η 2binding mode as in Rh(η 2 -dppe)(CO)Cl. [30][31][32] Reactions of metal carbonyl complexes of the type RhL 2 (CO)Cl with oxygen have received relatively little attention. Foote et al 33,34 demonstrated that reaction of Rh(PPh 3 ) 2 (CO)Cl with singlet oxygen at -40 °C forms an analogue of the well-known Vaska's adduct (η 2 -O 2 )-Ir(PPh 3 ) 2 (CO)Cl, [35][36][37][38] but the Rh complex rapidly loses its oxygen on warming to room temperature.…”

Section: Introductionmentioning

confidence: 99%

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Stoichiometric and Catalytic Oxidation of BINAP by Dioxygen in a Rhodium(I) Complex

et al. 2002

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The square planar complex (BINAP)Rh(CO)Cl (BINAP = 2,2‘-bis(diphenylphosphino)-1,1‘-binaphthyl) was synthesized from [Rh(COD)Cl]2 (COD = 1,5 cyclooctadiene) and BINAP under a CO atmosphere. It reacts with oxygen to form the square planar (BINAP(O))Rh(CO)Cl in approximately 50% yield, along with molar equivalents of free BINAP dioxide (BINAP(O)2) and CO2. The oxygen atom of the BINAP(O) was shown crystallographically to be trans to the CO ligand. In the presence of excess BINAP under CO/O2 gas mixtures, the reaction is catalytic with a TOF of 0.16 h-1 at ambient temperature in chloroform. The kinetics of this transformation were investigated and conditions for optimum selectivity for BINAP(O) formation suggested. A stoichiometric mechanism is proposed that involves initial formation of an O2 adduct, followed by oxygen atom transfer to both phosphorus atoms of BINAP or to one phosphorus atom and the CO ligand trans to it. These processes might be concerted, or stepwise with intermediate RhO species. To the best of our knowledge, this chemistry represents the first example of a reaction exhibiting oxygen atom addition from O2 either to both phosphorus atoms in a bisphosphine ligand or to one phosphorus atom and a CO ligand in the same complex.

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