Structure and chemistry of [RhX(ttp)]n+ complexes: trans influence and steric distortion effects on rhodium-phosphorus coupling constants and bond distances

Synthesis of the Chiral Triphosphine (S,S)-PhP(CH2CHMeCH2PPh2)2and Its Metal Complexes

“…The overall geometry around rhodium is square planar. The Rh−Cl and Rh−P bond distances are within the range observed for similar complexes RhCl(ttp) and RhCl(etp) . The coordination sphere is similar to that reported for RhCl(ttp) except that the bond distances between rhodium and two terminal phosphorus differ significantly by 0.028 Å in the chiral complex RhCl(ttp*) but are the same by symmetry in RhCl(ttp) and that the angles between P(1)−Rh−P(2) and P(3)−Rh−P(2) are different by 3.3° in the chiral complex RhCl(ttp*) but are identical in RhCl(ttp).…”

New Tridentate Phosphine Rhodium and Iridium Complexes, Including a Stable Rhodium(I) Silyl. Si−S Activation and a Strong Effect of X in (PP2)M−X (X = H, Cl, Me) on Si−H Activation

“…The crystal structure of 5 (Figure , Table ) exhibits a considerable distortion from square planarity, the angles between the trans-disposed ligands being substantially smaller than 180°. A similar distortion was observed in a series of Rh(I) compounds having a similar triphosphine ligand, PhP(CH 2 CH 2 CH 2 PPh) 2 (PP 2 *) . It was shown that the tetrahedral distortion from planar geometry of PP 2 *RhX complexes depends on the bulk of the X ligand: for X = Cl, Py, PEt 3 , the average angles between the trans - disposed ligands are 175, 164, and 156°, respectively.…”

Mononuclear ruthenium complexes containing two different phosphines in trans position: I. Synthesis and spectroscopic characterization

“…The conversion is 100% after 6 h. It is interesting to observe that a shorter time (2 h) has been sufficient for the formation of the complex 1a, in agreement with P(p-CH 3 OC 6 H 4 ) 3 easier coordination to the ruthenium due to the electron donating power of the CH 3 O substituent. A longer reaction time (14 days) is required to obtain the analogous complex containing the P(OPh) 3 in trans position to the P n Bu 3 , due to phosphito less basicity (pK a = À2). All Ru(CO) 2 (CH 3 COO) 2 (P n Bu 3 )[P(p-XC 6 H 4 ) 3 ] complexes (1a-1e) have been characterized by IR and multinuclear NMR spectroscopy and the collected data are in agreement with an octahedral structure containing two phosphines in trans position, two cis carbonyl groups and two cis acetato ligands (Fig.…”

“…New mononuclear ruthenium complexes Ru (CO) 3 , H, F, Cl), containing two different phosphinic ligands in trans position, have been synthesized and spectroscopically characterized. These complexes contain, in trans position to the P n Bu 3 , different para substituted triarylphosphinic ligands, having the same cone angle value, but different pK a values.…”

“…The ''trans effect'' is a well-known phenomenon for ligand substitution in square-planar complexes of Pt(II) [2], Rh(I) [3], Pd(II) and Ni(II) [4], while it has been much less investigated for octahedral complexes [5]. In particular, the ''trans influence'' has been well established for ruthenium octahedral silyl complexes [5o,5p,5q,6].…”