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Ruthenocene-based PCP tBu pincer ligands were used to synthesize novel pincer palladium chloride Rc F [PCP tBu ]PdCl ( 2a ) and two novel palladium tetrahydroborates Rc F [PCP tBu ]Pd(BH 4 ) ( 3a ) and Rc * [PCP tBu ]Pd(BH 4 ) ( 3b ), where Rc F [PCP tBu ] = κ 3 -{2,5-(tBu 2 PCH 2 ) 2- C 5 H 2 }Ru(Cp F ) (Cp F = C 5 Me 4 CF 3 ), and Rc*[PCP tBu ] = κ 3 -{2,5-(tBu 2 PCH 2 ) 2 C 5 H 2 }Ru(Cp*) (Cp* = C 5 Me 5 ). These coordination compounds were characterized by X-ray, NMR and FTIR techniques. Analysis of the X-ray data shows that an increase of the steric bulk of non-metalated cyclopentadienyl ring in 3a and 3b relative to non-substituted Rc[PCP tBu ]Pd(BH 4 ) analogue ( 3c ; where Rc[PCP tBu ] = κ 3 -{2,5-(tBu 2 PCH 2 ) 2 C 5 H 2 }Ru(Cp), Cp = C 5 H 5 ) pushes palladium atom from the middle plane of the metalated Cp ring in the direction opposite to the ruthenium atom. This displacement increases in the order 3c &lt; 3b &lt; 3a following the order of the Cp-ring steric volume increase. The analysis of both X-ray and IR data suggests that BH 4 ligand in both palladium tetrahydroborates 3a and 3b has the mixed coordination mode η 1,2 . The strength of the BH 4 bond with palladium atom increases in the order Rc[PCP tBu ]Pd(BH 4 ) &lt; Rc*[PCP tBu ]Pd(BH 4 ) &lt; Rc F [PCP tBu ]Pd(BH 4 ) that appears to be affected by both steric and electronic properties of the ruthenocene moiety.

Steric and Electronic Effect of Cp-Substituents on the Structure of the Ruthenocene Based Pincer Palladium Borohydrides