110140-35-7Relevant academic research and scientific papers
THE PREPARATION OF FROM AND PENTA-1,4-DIENE; CARBON-CARBON BOND FORMATION BY DEHYROGENATION
Mann, Brian E.,Manning, Paul W.,Spencer, Catriona M.
, p. C64 - C66 (1986)
reacts with penta-1,4-diene in CD2Cl2, to give initially 3-C5H9)RuCl(PPh3)2>.Dehydrogenation by an excess of pentadiene produces 5-C5H7)RuCl(PPh3)2>.When acetone is used as the dehydrogenating agent, then the rea
Half-sandwich ruthenium-phosphine complexes with pentadienyl and oxo- and azapentadienyl ligands
Reyna-Madrigal, Amira,Moreno-Gurrola, Anabel,Juarez-Saavedra, Patricia,Leyva-Ramirez, Marco A.,Paz-Sandoval, M. Angeles,Perez-Camacho, Odilia,Navarro-Clemente, M. Elena,Arif, Atta M.,Ernst, Richard D.
, p. 7125 - 7145,21 (2020/09/02)
Treatment of RuCl2(PPh3)3 and RuHCl(PPh3)3 with the tin compound CH2C(Me) CHC(Me)CH2SnMe3 gives the corresponding acyclic pentadienyl half-sandwich (η5-CH2C(Me)CHC(Me)CH 2)RuX(PPh3)2 [X = Cl, (2); H, (3)]. The steric congestion in 2 is most effectively relieved by formation of the cyclometalated complex (η5-CH2C(Me)CHC(Me)CH2)Ru(C 6H4PPh2)(PPh3) (4). Addition of 1 equiv of PHPh2 to (η5-CH2CHCHCHCH 2)RuCl(PPh3)2 (1) affords the chiral complex (η5-CH2CHCHCHCH2)RuCl(PPh 3)(PHPh2) (5), while compound (η5-CH 2C(Me)CHC(Me)CH2)RuCl(PPh3)(PHPh2)] (6) is directly obtained from the reaction of RuCl2(PPh 3)3 with CH2C(Me)CHC(Me)CH2Sn(Me) 3 and PHPh2. Treatment of RuCl2(PPh 3)3 with the corresponding Me3SnCH 2CH=CHCH=NR (R = Cy, t-Bu) affords (1-3,5-η-CH 2CHCHCHNCy)RuCl(PPh3)2 (7) and [1-3,5-η-CH2CHCHCHN(t-Bu)]RuCl(PPh3)2 (8). The hydrolysis of 7, on a silica gel chromatography column, allows the isolation of RuCl(η5-CH2CHCHCHO)(PPh3)2 (9). The azapentadienyl complex 7 reacts with 1 equiv of PHPh2 to afford [1-3,5-η-CH2CHCHCHN(Cy)]RuCl(PPh3)(PHPh 2) (10), while the corresponding product [1-3,5-η-CH 2CHCHCHN(t-Bu)]RuCl(PPh3)(PHPh2) (11) from 8 is only observed through 1H and 31P NMR spectroscopy as a mixture of isomers. Two equivalents of PHPh2 gives spectroscopic evidence of [η3-CH2CHCHCHN(t-Bu)]RuCl(PHPh 2)3. A mixture of products [η5-CH 2C(Me)CHC(Me)O]RuCl(PPh3)2 (12) and [η5-CH2C(Me)CHC(Me)O]RuH(PPh3)2 (13) is obtained from reaction of RuCl2(PPh3)3 with Li[CH2C(Me)CHC(Me)O]. In contrast, the oxopentadienyl compound 13 is cleanly formed from RuHCl(PPh3)3 and Li[CH 2C(Me)CHC(Me)O]. An attempt to separate compounds 12 and 13 by crystallization gives an orthometalated product [η5-CH 2C(Me)CHC(Me)O]Ru(C6H4PPh2)(PPh 3) (14), which is the oxopentadienyl analogue to 4. The bulky [1-3,5-η-CH2C(t-Bu)CHC(t-Bu)O]RuH(PPh3)2 (15) analogue to 13 has also been prepared from RuHCl(PPh3) 3 and Li[CH2C(t-Bu)CHC(t-Bu)O]. Compounds 3, 5, 6, 7, and 12-15 have been structurally characterized. The preferred heteropentadienyl orientations and the relative positions of the H, Cl, PPh3, and PHPh2 ligands have been established in the piano-stool structures for all compounds, and it can be definitively surmised that the chemistry involved in the heteropentadienyl half-sandwich compounds studied is dominated by steric effects.
Pentadienyl-metal-phosphine chemistry. 17. Syntheses, structures, and spectroscopy of pentadienyl-ruthenium-phosphine complexes
Bleeke,Rauscher
, p. 2328 - 2339 (2008/10/08)
The reaction of RuCl2(PPh3)3 with pentadienyltributyltin produces (η5-pentadienyl)RuCl(PPh3)2 (1), which serves as a convenient starting material for the synthesis of a large family of new pentadienyl-ruthenium-phosphine complexes. Treatment of 1 with 1 equiv of PMe3, PMe2Ph, PEt3, or PEt2Ph produces the mixed-phosphine complexes (η5-pentadienyl)RuCl(PR3) (PPh3) (2a, PR3 = PMe3; 2b, PR3 = PMe2Ph; 2c, PR3 = PEt3; 2d, PR3 = PEt2Ph). Compound 2c crystallizes in the monoclinic space group P21/c with a = 11.435 (2) A?, b = 13.770 (4) A?, c = 18.237 (5) A?, β = 109.04 (2)°, V = 2715 (1) A?3, and Z = 4. This complex adopts a pseudooctahedral coordination geometry with the PEt3 ligand residing under the open mouth of the pentadienyl ligand and the PPh3 and Cl groups lying under the pentadienyl edges . Treatment of 1 with 2 equiv of PEt3, PEt2Ph, or PEtPh2 produces (η5-pentadienyl)RuCl(PR3)2 (3c, PR3 = PEt3; 3d, PR3 = PEt2Ph; 3e, PR3 = PEtPh2). (η5-Pentadienyl)RuCl(PMe2Ph)2 (3b) is obtained cleanly by reacting 2b with one additional equivalent of PMe2Ph. (η5-Pentadienyl)RuCl(PEt3)2 (3c) [monoclinic, Cc, a = 28.094 (7) A?, b = 10.003 (2) A?, c = 15.134 (3) A?, β = 98.54 (2)°, V = 4205 (2) A?3, Z = 8] and (η5-pentadienyl)RuCl(PEt2Ph)2 (3d) [orthorhombic, P212121, a = 16.848 (7) A?, b = 19.409 (4) A?, c = 7.867 (1) A?, V = 2572 (1) A?3, Z = 4] have been structurally characterized. Both complexes adopt pseudooctahedral coordination geometries in which one phosphine resides under the pentadienyl mouth while the other phosphine and the chloro ligand lie under the pentadienyl edges . Treatment of 1 with 3 equiv of PMe3 produces (η3-pentadienyl)RuCl(PMe3)3 (4a). (η3-Pentadienyl)RuCl(PMe2Ph)3 (4b) is obtained upon treatment of 2b with 2 equiv of PMe2Ph. 4a crystallizes in the monoclinic space group P21/n with a = 9.628 (3) A?, b = 13.662 (3) A?, c = 15.667 (4) A?, β = 91.59°, V = 2060 (1) A?3, and Z = 4. 4a's coordination geometry is pseudooctahedral with C1 and C3 of the pentadienyl ligand, the three phosphorus atoms, and the chlorine atom occupying the six coordination sites. The η3-pentadienyl ligand adopts a W-shaped syn geometry. Both 4a and 4b react with Ag+O3SCF3- or Me+O3SCF3- to yield [(η5-pentadienyl)Ru(PR3)3] +O3SCF3- (5a, PR3 = PMe3; 5b, PR3 = PMe2Ph). 5a crystallizes in the monoclinic space group P21/m with a = 8.622 (2) A?, b = 11.302 (4) A?, c = 12.676 (2) A?, β = 103.22 (1)°, V = 1202.6 (6) A?3, and Z = 2. It exhibits pseudooctahedral coordination geometry with one PMe3 ligand under the open pentadienyl mouth and the other PMe3 ligands under the pentadienyl edges . Compounds 1, 3, and 5 undergo dynamic processes in solution involving rotation of their pentadienyl groups with respect to the metal-ligand framework. ΔG*'s for these processes have been determined from line-shape simulations of the variable-temperature 31P NMR spectra.
