Enantiomorphs of a carbene-ruthenium(II)-porphyrin complex with four 'chiral pillars'.

The chiral metalloporphyrin (dibenzoylmethylene-kappaC)(ethanol-kappaO){5,10,15,20-tetrakis[(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracen-9-yl]porphyrinato-kappa(4)N}ruthenium(II)-ethanol-dichloromethane (1/2/2), [Ru(C(84)H(76)N(4))(C(15)H(10)O(2))(C(2)H(6)O)].2C(2)H(6)O.2CH(2)Cl(2), and its enantiomorph were prepared from enantiomerically pure porphyrins. The enantiomers are potential versatile catalysts for asymmetric cyclopropanation, aziridination or epoxidation. In each compound, the rather large dibenzoylcarbene group is squeezed between four columnar 1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracen-9-yl groups at the meso positions resulting in a doming deformation of the porphyrin core. The dibenzoylcarbene group has an anti conformation. The benzoyl O atoms make short van der Waals contacts (< 2.6 A) with the methine groups of the chiral columnar substituents at the 10 and 20 positions of the porphyrin rings. A hydrogen-bonded supramolecular chain is formed parallel to the b axis by interactions between the benzoyl O atom and the hydroxy groups of the coordinated and uncoordinated ethanol molecules.

(5,10,15,20-Tetra-phenyl-porphyrinato-κN)(2,2,2-trifluoro-1-phenyl-ethyl-idene-κC)ruthenium(II): a stable fluorinated alkyl-idene complex of a ruthenium(II) porphyrin.

In the title compound, [Ru(C(44)H(28)N(4))(C(8)H(5)F(3))], the fluorin-ated alkyl-idene group is bound to a five-coordinate Ru atom, which is located toward the carbene C atom, 0.3301 (5)Šfrom the least-squares plane of the C(20)N(4) porphyrin core. The Ru=C bond is tilted slightly from the normal to the C(20)N(4) least-squares plane due to steric repulsion between the porphyrinate ligand and the bulky trifluoro-methyl group. The Ru=C bond length of 1.838 (2) Šis comparable with those in bis-(subsituted phen-yl)carbene analogs.

The first metalloporphyrin dimer linked by a bridging phenylenedicarbene ligand.

In the first bis[ruthenium(II)-porphyrin]-dicarbene complex, mu-[1,4-phenylenebis(phenylmethylidene-kappaC)]bis[(ethanol-kappaO)(5,10,15,20-tetra-p-tolylporphyrinato-kappa4N)ruthenium(II)] 1,2-dichloroethane trisolvate, [Ru2(C20H14)(C48H36N4)2(C2H6O)2].3C2H4Cl2, an inversion center is located at the center of the mu-phenylene group, leading to a parallel arrangement for the pair of porphyrin ring systems. The bond lengths and angles compare favourably with literature values for ruthenium-porphyrin-monocarbene complexes; the Ru=C(carbene) bond length and the C(phenyl)-C(carbene)-C(phenylene) angle are 1.865 (3) A and 112.3 (3) degrees , respectively. The Ru(II) ion is displaced out of the C20N4 porphyrin least-squares plane (by 0.2373 A) toward the bridging ligand of the Ci-symmetry dimer. The porphyrin ring systems of the dimer thus exhibit mildly domed conformations.

A five-coordinate ruthenium(II)-porphyrin-carbene complex: [bis(3-trifluoromethylphenyl)methylene-kappaC](5,10,15,20-tetra-p-tolylporphyrinato-kappa4N)ruthenium(II).

The stable title trifluoromethyl-substituted carbenyl metalloporphyrin, [Ru(C(15)H(8)F(6))(C(48)H(36)N(4))], has a five-coordinate Ru atom which is displaced from the porphyrin N(4) plane towards the axial carbene ligand by 0.230 (3) A. The Ru--C(carbene) bond coincides with a crystallographic twofold axis and its length of 1.841 (6) A is notably shorter than the value of 1.868 (3) A in the pyridine adduct.

The trans influence of the pyridine ligand on ruthenium(II)-porphyrin-carbene complexes.

In the two ruthenium(II)-porphyrin-carbene complexes (dibenzoylcarbenyl-kappaC)(pyridine-kappaN)(5,10,15,20-tetra-p-tolylporphyrinato-kappa(4)N)ruthenium(II), [Ru(C(15)H(10)O(2))(C(5)H(5)N)(C(48)H(36)N(4))], (I), and (pyridine-kappaN)(5,10,15,20-tetra-p-tolylporphyrinato-kappa(4)N)[bis(3-trifluoromethylphenyl)carbenyl-kappaC]ruthenium(II), [Ru(C(15)H(8)F(6))(C(5)H(5)N)(C(48)H(36)N(4))], (II), the pyridine ligand coordinates to the octahedral Ru atom trans with respect to the carbene ligand. The C(carbene)-Ru-N(pyridine) bonds in (I) coincide with a crystallographic twofold axis. The Ru-C bond lengths of 1.877 (8) and 1.868 (3) A in (I) and (II), respectively, are slightly longer than those of other ruthenium(II)-porphyrin-carbene complexes, owing to the trans influence of the pyridine ligands.

A ruthenium(II)-porphyrin-carbene complex with a weakly bonded methanol ligand.

The title diphenylcarbene porphyrin complex (diphenylcarbenyl-kappaC)(methanol-kappaO)(5,10,15,20-tetra-p-tolylporphyrinato-kappa(4)N)ruthenium(II) methanol solvate, [Ru(C(13)H(10))(C(48)H(36)N(4))(CH(4)O)].CH(4)O, has a six-coordinate Ru atom with a methanol molecule as the second axial ligand. The carbene fragment is slightly distorted from an ideal sp(2) configuration, with a C(phenyl)-C(carbene)-C(phenyl) angle of 112.2 (3) degrees. The Ru-C bond length of 1.845 (3) A is comparable with other carbene complexes. The two phenyl rings of the carbene ligand are perpendicular to the carbene plane. Methanol solvate molecules link the methanol ligands of adjacent porphyrin complexes via hydrogen bonds.