Water-Soluble Phosphines. 6.¹ Tailor-Made Syntheses of Chiral Secondary and Tertiary Phosphines with Sulfonated Aromatic Substituents:  Structural and Quantum Chemical Studies

Abstract

Chiral water-soluble secondary phosphines (2-6) were obtained by nucleophilic phosphination of FC(6)H(4)-4-SO(3)K (1a), FC(6)H(3)-2,4-(SO(3)K)(2) (1b), and FC(6)H(4)-2-SO(3)K (1c) with RPH(2) (R = Ph, 2,4,6-Me(3)C(6)H(2), 2,4,6-iPr(3)C(6)H(2)) in the superbasic medium DMSO/KOH by employing steric control of substitution at phosphorus by bulky substituents R and sulfonic groups in the ortho position of the aromatic ring systems in 1b or 1c. The secondary phosphines may be deprotonated in DMSO/KOH to give phosphido anions which on reaction with alkyl halides (PhCH(2)Cl, Br(CH(2))(3)Br, and C(12)H(25)Br) yield mono- or bidentate tertiary phosphines (7-10). Ligands of this type are alternatively accessible by nucleophilic arylation of secondary phosphines, e.g. Ph(Me)PH or Ph(H)P(CH(2))(3)P(H)Ph with 1a or 1b, respectively. The crystal structure of the starting material 1b.H(2)O (space group P2(1)/m) has been determined. In the solid state of 1b.H(2)O the individual molecules are interconnected by ionic interactions between the potassium cations and the SO(3)(-) anions. The C-F bond (C(1)-F 1.347(4) Å) is shorter than that in C(6)H(5)F (1.356(4) Å). The unit cell of 7a.0.5H(2)O (space group P&onemacr;), the first structurally characterized chiral phosphine with a sulfonated phenyl substituent, contains the two enantiomers. Due to the asymmetrical substitution at phosphorus the PC(3) skeletons are significantly distorted (P(1)-C(1,11,31) 1.864(10), 1.825(8), 1.841(7) Å). The electronic structure of sulfonated fluorobenzenes FC(6)H(5)(-)(n)()(SO(3)M)(n)() (M = K, NH(4), n = 1-3) is discussed on the basis of quantum chemical calculations. In particular, the reactivity difference toward nucleophilic phosphination within the series is rationalized in terms of steric factors and of the -I effect of the sulfonic groups.

Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH2-, COOH- und P(O)(OR)2-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH2, COOH and P (O)(OR)2 Functionalized Side Chains

“…Für die Synthese von Liganden des Typs C und D boten sich prinzipiell zwei verschiedene Syn thesewege an: 1) die Einführung der Phosphanogruppierung in Derivate der Halogenphenylessigsäuren, Halogenbenzylamine oder Halogenbenzylphosphonsäuren durch nucleophile Phosphanierung mit Alkalimetallphosphiden [8] oder durch metallkatalysierte P-C-Kupplung mit primären oder sekundären Phosphanen [9] sowie 2) die Additi on von Phosphiten oder sekundären Phosphanoxiden an Formyl-oder Acetylderivate des PPh3. Die große Anwendungsbreite der beiden unter Punkt 1 aufgeführten Verfahren konnte im Rahmen eige ner Arbeiten an zahlreichen Beispielen demonstriert werden.…”

Water-Soluble Tripodal Phosphane Ligands and Their Rhodium Complexes

“…The synthesis of the water-soluble tripodal phosphane ligand tionalized tripodal ligand 6 react with Rh(PPh 3 ) 3 (CO)H to form the water-soluble and water-insoluble rhodium carbocis,cis 3, 3, (OCH 2 CH 2 ) x OCH 3 ]C 6 H 6 (x = 30Ϫ160) (5) has been achieved in a four-step reaction senyl hydrido complexes 5a and 6a, respectively. The catalytic activity of the rhodium complex 5a in the hydroformylation quence.…”

“…The catalytic activity of the rhodium complex 5a in the hydroformylation quence. The alcohol Mo(CO) 3 [cis,cis-1,3,5-(PPh 2 ) 3 -1,3,5-(CH 2 OH) 3 C 6 H 6 ] (1) is converted to the corresponding alcoof 1-hexene was found to be comparable in a single-phase system (1-hexene/methanol) with that in the biphasic system holate 2, which forms the polyethylene glycol derivative 3 in a polyaddition reaction with oxirane. After methylation of the (1-hexene/water).…”

“…Thus, only one used without further purification. The molybdenum complex 1 [11] , the ligand 6 [11] and Rh(PPh 3 ) 3 (CO)H [17] were prepared as described set of resonances for the ring methylene and quaternary car- 3,3, ethoxymethyl)cyclohexane (5): A solution of 0.5 mmol of 4 in 150 ml of THF and 5 ml of an aqueous solution of K 2 CO 3 (2.0 ) were Tricarbonyl [cis,cis-1,3,5-tris(diphenylphosphanyl)-1,3,5-tris(hy-placed in a double-walled Duran Schlenk tube and the mixture was droxypolyethoxymethyl)cyclohexane]molybdenum (3): A steel autodegassed by using the freeze-pump-thaw technique. The vigorously clave fitted with a Teflon inlet was charged with a suspension of stirred solution was cooled to 15°C (cooling solvent: water) and 907 mg (1.0 mmol) of 1 and 72 mg (3.0 mmol) of NaH in 120 ml dinitrogen monoxide (N 2 O) was added (1.0Ϫ1.3 bar).…”

“…The salts moved under reduced pressure and the colorless to off-white, vis-(NaCl and residual NH 4 Cl) were filtered off by passage through cous oil was dried in vacuo (12 h at 60°C (br. s,orCarbonylhydrido[cis,3,3, [cis,cis-1,3,5-tris(diphenylphosphanyl)-1,3,5-tris-under reduced pressure (0.1Ϫ0.5 mbar). The PPh 3 sublimed during (methoxypolyethoxymethyl)cyclohexane]molybdenum (4): A mixthe course of the reaction.…”