Diruthenium Complexes with a 1,8-Naphthyridine-based Bis(silyl) Supporting Ligand: Synthesis and Structures of Complexes Containing Ru^II₂(μ-H)₂ and Ru^I₂ Cores

Persistence of a Ru3(μ‐CO)3(CO)5Cluster Bound to a PNNP “Expanded Pincer” Ligand in Different Protonation States

“…We reason that the rigid triruthenium carbonyl cluster prevents the Ru site in the dearomatized pocket to function as a Lewis acid as is the case in 16 valence electron mononuclear PNP*Ru complexes. [6a] 6), Ru1À Ru3 2.8717(6), Ru2À Ru3 2.8394(6), Ru1À P1 2.3403 (15),Ru1À N1 2.186(4),Ru2À P2 2.3390(14),Ru2À N2 2.193(4), C1À C2 1.347( 9), C9À C10 1.460 (9). Scheme 4.…”

“…Previous work showed that this reversible dearomatization enables the heterolytic cleavage of H 2 using a combination of MMC and MLC. [8a] Inspired by work from Tobita et al [9] on the use of Ru 3 (CO) 12 as a precursor for the synthesis of 1,8-naphthyridine-based bimetallic complexes, we set out to synthesize diruthenium carbonyl complexes of the tBu PNNP ligand. Unexpectedly, we obtained complexes of the expanded pincer ligand containing an intact triruthenium carbonyl cluster, prompting us to investigate the possibility of H 2 activation on this trinuclear cluster through MLC.…”

“…Previous work showed that this reversible dearomatization enables the heterolytic cleavage of H 2 using a combination of MMC and MLC [8a] . Inspired by work from Tobita et al [9] . on the use of Ru 3 (CO) 12 as a precursor for the synthesis of 1,8‐naphthyridine‐based bimetallic complexes, we set out to synthesize diruthenium carbonyl complexes of the t Bu PNNP ligand.…”

“…Two potassium ions are shown, indicating the structure of the coordination polymer. Selected bond distances (Å): Ru1À Ru2 2.7217(6), Ru1À Ru3 2.8717(6), Ru2À Ru3 2.8394(6), Ru1À P1 2.3403(15), Ru1À N1 2.186(4), Ru2À P2 2.3390(14), Ru2À N2 2.193(4), C1À C2 1.347(9), C9À C10 1.460(9).…”