Correlation between Structural and Solution Calorimetric Data for Cp*Ru(PR₃)₂Cl (Cp* = C₅Me₅) Complexes

Abstract

Single-crystal X-ray diffraction studies were conducted on the following compounds: Cp*Ru(PMe 3 ) 2 Cl (1), Cp*Ru(PPhMe 2 ) 2 Cl (2), Cp*Ru(PMePh 2 ) 2 Cl (3), Cp*Ru(PPh 3 ) 2 Cl (4), Cp*Ru(PEt 3 ) 2 Cl (5), Cp*Ru(AsEt 3 ) 2 Cl (6), Cp*Ru(P n Bu 3 ) 2 Cl (7), and Cp*Ru(dmpm)Cl (8). Structural information obtained from these X-ray studies can be correlated with enthalpies of ligand substitution previously determined from solution calorimetry. The cone angle of the phosphine ligand (monodentate) and the Ru-P bond distance were found to be proportional to the enthalpy of reaction.

Ruthenium vs. Osmium Complexes as Catalysts for Atom Transfer Radical Addition Reactions

“…The Os–Br bond lengths [2.5110(9) and 2.4955(8) Å] of the Os III complex 2 are shorter than that found for the Os II complex 3 [2.5934(4) Å]. A similar shortening has been observed for the analogous Ru complexes [Cp*RuCl 2 (PPh 3 )] [Ru–Cl 2.4042(5) and 2.3775(5) Å]6a and [Cp*RuCl(PPh 3 ) 2 ] [Ru–Cl 2.4583(6) Å] 14…”

“…The Os-Br and Os-P bond lengths observed for 3 (Figure 1) are very similar to those found for the analogous complex [CpOsBr(PPh 3 ) 2 ] (Cp = η 5 -cyclopentadienyl). [13] The Os-Br bond lengths [2.5110(9) and 2.4955 (8) [14] We have also investigated the reduction of the complexes 1 and 2 with Mg in the presence of an excess of styrene (Scheme 2). This experiment was performed to evaluate the possibility that the hypothetical intermediates [Cp*MX(PPh 3 )] are stabilized by coordination to the olefinic substrate.…”

Correlations among 31P NMR Coordination Chemical Shifts, Ru–P Bond Distances, and Enthalpies of Reaction in Cp′Ru(PR3)2Cl Complexes (Cp′ = η5-C5H5, η5-C5Me5; PR3 = PMe3, PPhMe2, PPh2Me, PPh3, PEt3, PnBu3)

“…Ruthenium phosphine complexes show great utility and promise as catalysts. , Experimental Ru–P bond enthalpies and distances give insight into metal–phosphine bonding . Nolan and co-workers measured Ru–P bond enthalpies in Cp′Ru­(PR 3 ) 2 Cl complexes, where Cp′ is either the cyclopentadienyl (Cp, C 5 H 5 ) or pentamethylcyclopentadienyl (Cp*, C 5 Me 5 ) ligand . Ru–P bond distances are known for CpRu­(PR 3 ) 2 Cl with PR 3 = PMe 3 ( 1 ), PPhMe 2 ( 2 ), PPh 2 Me ( 3 ), PPh 3 ( 4 ), PEt 3 ( 5 ) but not for CpRu­(P n Bu 3 ) 2 Cl ( 6 ).…”

Hydrology of hillslope‐wetland streams, Polar Bear Pass, Nunavut, Canada

“…Die Ru1‐As1‐Bindung (2.4023(8) Å) ist kürzer als Ru‐As‐Bindungen in Komplexen mit dem starken σ‐Donor‐ und schwachen π‐Akzeptorliganden AsPh 3 (2.412(1) Å in [CpRu(CO)(AsPh 3 )Cl],14 2.442(1) Å und 2.449(1) Å in [Cp*Ru(AsPh 3 ) 2 Cl]15 und 2.435(1) Å in [CpRu(MeCN) 2 (AsPh 3 )] + [16] ). Das As 4 ‐Tetraeder in 1 ist sterisch durch den Cp*‐Liganden sowie durch zwei der vier Phenylsubstituenten des dppe‐Liganden abgeschirmt.…”