Different Reactivities of (5-Ph 2 P-Ace-6-) 2 MeSiH toward the Rhodium(I) Chlorides [(C 2 H 4 ) 2 RhCl] 2 and [(CO) 2 RhCl] 2 . Hirshfeld Atom Refinement of a Rh–H···Si Interaction

Holsten, Sebastian; Malaspina, Lorraine A.; Kleemiss, Florian; Mebs, Stefan; Hupf, Emanuel; Grabowsky, Simon; Beckmann, Jens (2021). Different Reactivities of (5-Ph 2 P-Ace-6-) 2 MeSiH toward the Rhodium(I) Chlorides [(C 2 H 4 ) 2 RhCl] 2 and [(CO) 2 RhCl] 2 . Hirshfeld Atom Refinement of a Rh–H···Si Interaction. Organometallics, 40(13), pp. 2027-2038. American Chemical Society 10.1021/acs.organomet.0c00804

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The reaction of (5-Ph2P-Ace-6-)2MeSiH with [(C2H4)2RhCl]2 proceeded via elimination of ethylene and oxidative addition of the Si–H bond at rhodium and provided the rhodium(III) complex (5-Ph2P-Ace-6-)2MeSiRh(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-Ph2P-Ace-6-)2MeSiH with [(CO)2RhCl]2 occurred via elimination of hydrogen chloride and produced the rhodium(I) complex (5-Ph2P-Ace-6-)2MeSiRh(CO)2 (2).

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