Promoting π-Facial Interactions in Phenyl-Substituted 1,8-Bis(silylamido)naphthalene Alkaline Earth Complexes DOI Creative Commons

Matthew D. Haynes,

Clement G. Collins Rice, Louis J. Morris

et al.

Organometallics, Journal Year: 2025, Volume and Issue: 44(4), P. 582 - 594

Published: Feb. 5, 2025

Bimetallic 1,8-bis(silylamido)naphthalene alkaline earth complexes [(R3L)Ae]2 ([R3L]2– = [1,8-{(R3Si)N}2C10H6)]2–, where R3 Ph2Me, Ae Ca (1), Sr (2), and Ba (3); Ph3, (4), (5), (6) were prepared via protonolysis reactions of the phenyl-substituted proligands Ph3LH2 Ph2MeLH2 with [AeN″2]2 (N″ [N(SiMe3)2]−) in benzene. X-ray crystallographic analysis showed that 1, 2, 4 crystallize as nitrogen-bridged dimers. Conversely, 5 6 display a naphthalene-bridged motif, while structure 3 is intermediate between two distinct classes. NMR spectroscopic isolated samples 1–6 thf-d8 confirmed their conversion into monomeric adducts [(R3L)Ae(thf-d8)n]; verification structural motif was provided by crystal [(Ph3L)Sr(thf)3] (7). The range dimers influenced electron-withdrawing nature phenyl substituents ligand ability to form "soft" multihaptic π-facial interactions metal ions, which preferential for larger Sr2+ Ba2+ cations well relative strength metal-N bonds. This has been rationalized through complementary computational studies. work provides insight bonding preferences heavy rigid bis(amido) ligands.

Language: Английский

Heavier alkaline earth and heterobimetallic s-block “ate” complexes of a di(amido)siloxane ligand: solid-state structure and dynamic solution-phase behaviour DOI Creative Commons

Matthew D. Haynes,

Andrea O’Reilly, Alan F. Poole

et al.

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Heavy alkaline earth and heterobimetallic s-block “ate” complexes.

Language: Английский

Citations

1
Promoting π-Facial Interactions in Phenyl-Substituted 1,8-Bis(silylamido)naphthalene Alkaline Earth Complexes DOI Creative Commons

Matthew D. Haynes,

Clement G. Collins Rice, Louis J. Morris

et al.

Organometallics, Journal Year: 2025, Volume and Issue: 44(4), P. 582 - 594

Published: Feb. 5, 2025

Bimetallic 1,8-bis(silylamido)naphthalene alkaline earth complexes [(R3L)Ae]2 ([R3L]2– = [1,8-{(R3Si)N}2C10H6)]2–, where R3 Ph2Me, Ae Ca (1), Sr (2), and Ba (3); Ph3, (4), (5), (6) were prepared via protonolysis reactions of the phenyl-substituted proligands Ph3LH2 Ph2MeLH2 with [AeN″2]2 (N″ [N(SiMe3)2]−) in benzene. X-ray crystallographic analysis showed that 1, 2, 4 crystallize as nitrogen-bridged dimers. Conversely, 5 6 display a naphthalene-bridged motif, while structure 3 is intermediate between two distinct classes. NMR spectroscopic isolated samples 1–6 thf-d8 confirmed their conversion into monomeric adducts [(R3L)Ae(thf-d8)n]; verification structural motif was provided by crystal [(Ph3L)Sr(thf)3] (7). The range dimers influenced electron-withdrawing nature phenyl substituents ligand ability to form "soft" multihaptic π-facial interactions metal ions, which preferential for larger Sr2+ Ba2+ cations well relative strength metal-N bonds. This has been rationalized through complementary computational studies. work provides insight bonding preferences heavy rigid bis(amido) ligands.

Language: Английский

Citations

0