Preparation and Nuclear Magnetic Resonance Study of Phosphorus Compounds Containing Alkenyl Functional Groups

Abstract

The phosphines PPh,,(CH,CH,CH=CH,)3-n, n = 2-0, PPh,,(CH,CH2CH2CH=CH2),-,,, n = 1 or 2, and PPh,CH,CH=CH, have been synthesized and studied by ' H and ,'P magnetic resonance. The n.m.r. spectra of PPh,(OCH,CH=CH2), its oxide, O=PPh,(OCH,-CH=CH,), and its Arbuzov rearrangement product, 0=PPh2(CH2CH=CH2), have been investigated by ,'P decoupling of the proton spectrum, selective proton decoupling of the ,'P spectrum, and comparison with computer-simulated spectra to determine the spin-spin coupling constants. The n.m.r. spectra of the related oxides O=PPh,CH,CH,CH=CH,, O=P-(CHZCH2CH=CH2),, and O=P(OCH,CH=CH,), are also assigned. The data indicate that ,JPH > ,JpH for alkenylphosphines, 2Jp,, is larger for phosphine oxides than for phosphines, and ,Jell is little changed in comparing phosphorus(II1) with phosphorus(V) compounds.On a synthktise les phosphines PPh,,(CH2CH2CH=CH2),-,,, ti = 2-0,

Closo and hyper-closo ten-vertex ruthenacarboranes containing chelating alkenylphosphine ligands

“…These alkenyl signals were assigned by assuming that the magnitudes of trans- Figure 1 vicinal couplings (J 2 -3 ) remain larger than the corresponding cis-couplings (11-3 ) upon complexation of the alkenyl group to ruthenium. The alkenyl coupling constants of IIa-g were smaller than those in the free ligands 8 ' 13 ' 1 4 and similar to those found in other transition metal complexes containing chelating alkenyl phosphines or arstnes. 1 3 -]6 In the Q 3 C{ H} NMR spectra, the alkenyl carbons of IIa-g appeared approximately 42 to 60 ppm upfield from…”

“…8 The presence of two exchange processes was more evident in the variable temperature 3 The variable temperature 1H and 13 C{ 1 H} FTNMR spectra of IVa were also complicated due to the overlap of the temperature domains of the two dynamic processes.…”

Synthesis of New Half‐Sandwich Ruthenium(II) Complexes Bearing Alkenyl‐ and Alkynylphosphane Ligands

“…Solvents were dried by standard methods and distilled under nitrogen before use. The compounds [RuCl(η 5 -C 9 H 7 )(PPh 3 ) 2 ], [23] [RuI(η 5 -C 9 H 7 )(CO) 2 ], [24] Ph 2 PCH 2 -CH=CH 2 , [25] Ph 2 PCH 2 CH 2 CH=CH 2 , [26] and Ph 2 PCϵCPh [27] were prepared by previously reported methods. Infrared spectra were recorded with a Perkin-Elmer 1720-XFT or a Perkin-Elmer 599 IR spectrometer.…”

Mononuclear ruthenium(II) complexes bearing the (S,S)-iPr-pybox ligand

“…The structure exhibits a distorted octahedral geometry around the ruthenium atom which is bonded to the three nitrogen atoms of i Pr-pybox ligand, the carbon atom of the cyclohexylisocyanide group and two chlorine atoms. The chlorine atoms are located in a trans disposition with an angle value Cl(1)eRueCl(2) of 179.61 (5) . The cyclohexylisocyanide group presents a slightly distorted linear arrangement (Ru(1)eC (18)eN(4) of 175.7(5) ), this angle value as well as the distances ruthenium-carbon isocyanide (Ru(1)eC(18), 1.955(5) Å) and C^N (C(18)eN(4), 1.144(6) Å) are in the range found for other ruthenium (II)-isocyanide complexes [16].…”

“…Therefore, herein the synthesis of ruthenium(II) complexes containing the enantiopure (S,S)-i Pr-pybox ligand is reported. [4] and the phosphine PPh 2 CH 2 CH]CH 2 [5] were prepared by reported methods. Infrared spectra were recorded on a PerkineElmer 1720-XFT spectrometer.…”