Different Reactivities of (5-Ph₂P-Ace-6-)₂MeSiH toward the Rhodium(I) Chlorides [(C₂H₄)₂RhCl]₂ and [(CO)₂RhCl]₂. Hirshfeld Atom Refinement of a Rh–H···Si Interaction

Abstract

The reaction of (5-Ph 2 P-Ace-6-) 2 MeSiH with [(C 2 H 4 ) 2 RhCl] 2 proceeded via elimination of ethylene and oxidative addition of the Si−H bond at rhodium and provided the rhodium(III) complex (5-Ph 2 P-Ace-6-) 2 MeSiRh(H)Cl (1) possessing a reverse agostic interaction of the type Rh−H•••Si, which was characterized by Hirshfeld atom refinement (HAR) of single-crystal X-ray diffraction data. This technique allows the precise and accurate determination of hydrogen positions also for heavier transition-metal hydrides. The bonding situation in the Rh−H•••Si interaction was further analyzed using a set of complementary bonding indicators, such as the compliance matrix analysis or real-space bonding indicators derived from the electron and electron pair densities. The reaction of (5-Ph 2 P-Ace-6-) 2 MeSiH with [(CO) 2 RhCl] 2 occurred via elimination of hydrogen chloride and produced the rhodium(I) complex (5-Ph 2 P-Ace-6-) 2 MeSiRh(CO) 2 (2).

Tetrelanes versus Tetrylenes as Precursors to Transition Metal Complexes Featuring Tridentate PEP Tetryl Ligands (E=Si, Ge, Sn)

“…The acenaphthyl‐derived diphosphane‐silane G , which was prepared by treating 5‐diphenylphosphinoacenaphth‐6‐yl lithium with SiCl 2 MeH, [62] reacted differently with [Rh 2 Cl 2 (CO) 4 ] and [Rh 2 Cl 2 (C 2 H 4 ) 4 ] (Scheme 4). While the former gave the rhodium(I) dicarbonyl derivative [Rh(PSi Me P G )(CO) 2 ], the latter afforded a rhodium(III) complex, [RhHCl(PSi Me P G )] [63] …”

“…While the former gave the rhodium(I) dicarbonyl derivative [Rh(PSi Me P G )(CO) 2 ], the latter afforded a rhodium(III) complex, [RhHCl(PSi Me P G )]. [63] All PGeP tridentate germyl complexes that have thus far been prepared from metal-free germanes have used germanes of type H (Table 4), [51,[64][65][66][67][68][69][70][71] structurally analogous to silanes of type C. In all cases, germanes H were prepared by reacting Li[(o-C 6 H 4 )PR' 2 ] with the appropriate dichloridogermane. Interestingly, the oxidative addition of the GeÀ H bond of hydridogermanes to low-valent metal complexes [64,65] could not be satisfactorily achieved in most cases.…”

Hirshfeld Atom Refinement of Metal–Organic Complexes: Treatment of Hydrogen Atoms Bonded to Transition Metals

“…Due to the enumerated obstacles, up until our study, which was presented in a short communication, only six structures of complexes with TM–H bonds have been successfully refined with HAR; ,, complementary neutron data is available for only two of these. Our preliminary study extended the list of successful HARs by four structures with both X-ray and neutron diffraction data available.…”

“…Relativistic effects become particularly important for TMs starting from period VI since, for heavier elements, electrons attain higher velocities, which are a significant fraction of the velocity of light. A few X-ray structures containing TM atoms have been refined with HAR and Hamiltonian including relativistic effects, ,,− and only one of them was a TM-bound hydride . The latter compound was an osmium hexahydride compound for which high-resolution X-ray data was collected; however, high-resolution data did not bring any improvement compared to the data cut to the standard resolution for the Os–H bonds.…”

Influence of modelling disorder on Hirshfeld atom refinement results of an organo-gold(I) compound

“…The detected partial disorder of one phenyl ring was not included, since it was impossible to handle disorder with HAR in the software Tonto. Very recently, Kleemiss et al (2021) proposed how to model disorder in HAR using NoSpherA2 implemented in Olex2 (Holsten et al, 2021). Since then, the HAR method can be applied for structures with a higher degree of complexity of disorder, including cases where heavy atoms are present or for polymeric structures.…”