2010
DOI: 10.1016/j.jorganchem.2010.03.006
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Phosphine- and thiophosphorane-amine ligands: Lithiation and coordination to Rh(I)

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Cited by 26 publications
(21 citation statements)
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“…For the structure elucidation in solution, the most characteristic feature of 2 Li is the phosphorus NMR signal, only slightly downfield-shifted compared to 1 Li by the coordination at rhodium (Δδ = 9.1 ppm), but split into a doublet. The one-bond 31 P-103 Rh coupling constant of 146.5 Hz is similar to that found in the neutral [Rh(COD)(Ph 2 PCH 2 COO)] chelate complex (δ 31 P = 9.4 ppm, 1 J PRh = 146.4 Hz) [5d], in [RhCl(COD)(Cy 2 PCH 2 NHPh-κP)] (δ 31 P = 24.0 ppm, 1 J PRh = 145.5 Hz) [8], or in [RhCl(COD)(triarylphosphine-κP)] complexes (147.2 to 154.1 Hz) [7b]. A characteristic for 2 Li is also the strong upfield coordination shifts of the 13 C signals in α-position to phosphorus, Δδ = −6.9 and −9.6 for PCHN and C q 3a, respectively, and the increased 1 J PC coupling constant of C q 3a in the complex (37.2 Hz vs. 11.9 Hz in 1 Li ) while other 13 C (Δδ b 3 ppm) or proton NMR data of the benzazaphospholine ligand and Rh-coordinated 1,5-COD change much less and are found in the usual ranges.…”
supporting
confidence: 69%
See 1 more Smart Citation
“…For the structure elucidation in solution, the most characteristic feature of 2 Li is the phosphorus NMR signal, only slightly downfield-shifted compared to 1 Li by the coordination at rhodium (Δδ = 9.1 ppm), but split into a doublet. The one-bond 31 P-103 Rh coupling constant of 146.5 Hz is similar to that found in the neutral [Rh(COD)(Ph 2 PCH 2 COO)] chelate complex (δ 31 P = 9.4 ppm, 1 J PRh = 146.4 Hz) [5d], in [RhCl(COD)(Cy 2 PCH 2 NHPh-κP)] (δ 31 P = 24.0 ppm, 1 J PRh = 145.5 Hz) [8], or in [RhCl(COD)(triarylphosphine-κP)] complexes (147.2 to 154.1 Hz) [7b]. A characteristic for 2 Li is also the strong upfield coordination shifts of the 13 C signals in α-position to phosphorus, Δδ = −6.9 and −9.6 for PCHN and C q 3a, respectively, and the increased 1 J PC coupling constant of C q 3a in the complex (37.2 Hz vs. 11.9 Hz in 1 Li ) while other 13 C (Δδ b 3 ppm) or proton NMR data of the benzazaphospholine ligand and Rh-coordinated 1,5-COD change much less and are found in the usual ranges.…”
supporting
confidence: 69%
“…The Rh-Cl bonds, ranging from 2.3979(6) [Rh3-Cl3] to 2.4080(6) Å [Rh2-Cl2], are likewise lengthened by bridging to Li + whereas the Rh-P bonds (2.3128 (7) [Rh3-P3]-2.3245(7) Å [Rh4-P4]) are slightly shortened compared to the respective bonds in the related [(3-tert-butyl-1-neopentyl-2-trimethylsilyl-1,3-benzazaphospholine-κ 1 P)Rh(COD)Cl] complex (Rh-Cl 2.3832(6) and Rh-P 2.3354(5) Å [1a]). The bond lengths and angles of the (3-tertbutyl-1-neopentyl benzazaphospholine and Rh(1,5-COD) fragments of 2 Li (for selected data see [8]. In the only crystallographically characterized phosphinoacetate rhodium complex (to the best of our knowledge) mer-[RhCl(H)(Ph 2 CH 2 COO-κP,O)(Ph 2 CH 2 COOH-κP) 2 ], the transition metal is trivalent and displays longer Rh-Cl and shorter Rh-P bonds of 2.488(7) and 2.244(7)-2.396(7) Å, respectively [5c].…”
mentioning
confidence: 99%
“…Stepwise addition of two equiv of cyclohexylmagnesium chloride followed by methylmagnesium bromide and elemental sulfur afforded 1 as colorless solid in 72 % yield (Scheme 1). [12] Deprotonation of the methyl group of 1 with n-butyllithium was accomplished at room temperature. Subsequent treatment with diphenylchlorophosphine and oxidation with elemental sulfur furnished the bis(thiophosphinoyl)methane 2 as colorless crystalline solid in good yields of 67 %.…”
Section: Resultsmentioning
confidence: 99%
“…[5b] Overall, the P À C bond lengths are comparable to those found in the di-Scheme 3. (7), P2ÀS2 2.0105(8), P2ÀZr 3.1508(6), S1ÀZr 2.7502(6), S2ÀZr 2.7519 (7); P2-C13-P1 143.02 (12), P2-C13-Zr 105.68(9), P1-C13-Zr 107.87(9), C13-P1-S1 100.40 (7), C13-P2-S 103.20 (7), P1-S1-Zr1 82.70(2), P2-S2-Zr1 81.23 (2) (1); P1-C13-P2 141.3(2), S2-Pd1-S1 158.55(3), C13-Pd1-P3 177.72 (7), C13-Pd1-S2 80.13(8), C13-Pd1-S1 80.77(8), P3-Pd1-S1 98.65(3), P3-Pd1-S2 100.05(3).…”
Section: Resultsunclassified
“…These NMR data are in good accordance with those of 4c, prepared from Ph 2 PCH 2 OH and tBuNH 2 . 37 Air oxidation led slowly Table 2 Crystal and structure refinement data for 1b$1.43MeOH and 1h$MeOH. 1b$1.43MeOH contains two crystallographic sites, which are occupied with methanol molecules.…”
Section: Generalmentioning
confidence: 99%