Abstract
Reactions of [RuCl2(p-cymene)]2 with (tBu2PCH2CH2)2O (POP-tBu) and (iPr2PCH2CH2)2O (POP-iPr) afforded RuCl2(POP-tBu) (1) and [Ru2(μ-Cl)3(POP-iPr)2]Cl (2·Cl), respectively. The POP ligand is coordinated in a mer fashion in complex 1, whose crystal structure revealed a γ-agostic C−H···Ru interaction of one tBu group. Spectroscopic evidence indicated that this agostic interaction is retained in 1 in solution. A related compound, [Ru(N2)Cl(POP-tBu)]BPh4 (4), which also showed agostic bonding of a tBu group, was obtained by substitution of N2 for Cl- in 1, in the presence of NaBPh4. Compound 2·Cl readily underwent ion exchange with LiBPh4 or LiPF6 to give 2·BPh4 or 2·PF6 salts, respectively. A crystallographic analysis of 2·PF6 established a co-facial bioctahedral geometry of the [Ru2(μ-Cl)3(POP-iPr)2]+ cation containing two POP ligands coordinated in a fac fashion. Reactions of 1 and 2 with H2 afforded the dihydrogen complexes cis,trans-Ru(H2)Cl2(POP-tBu) (3) and cis,cis-Ru(H2)Cl2(POP-iPr) (5), respectively. The H−H bond distances are very similar in both compounds, r(H−H) = 1.0 ± 0.1 Å, based on the T1min and JHD data and results of DFT calculations. Reaction of 2 with N2 gave the dinitrogen complex cis,cis-Ru(N2)Cl2(POP-iPr) (6), but solutions of 1 under a nitrogen atmosphere showed no evidence of an analogous compound. The different steric requirements of the phosphorus substituents of the POP ligands were identified as the source of the differences in the coordination properties of the POP-tBu and POP-iPr complexes 1−6.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
