Heterometallic Second-Row Transition Metal Chain Compounds in Two Charge States: Syntheses, Properties, and Electronic Structures of [Mo-Mo-Ru] super(6+/7+) Chains

• Published in: Inorganic chemistry Vol. 54; no. 15; pp. 7660 - 7665
• Main Authors: Brogden, David W, Berry, John F
• Format: Journal Article
• Language: English
• Published: 03.08.2015
• Subjects: Bonding; Chains; Density functional theory; Elongation; Mathematical analysis; Molybdenum; Orbitals; Transition metals
• ISSN: 0020-1669
• DOI: 10.1021/acs.inorgchem.5b01370

Reaction of Mo sub(2)(dpa) sub(4) (dpa = 2,2'-dipyridylamido) with [1/2] equiv of [Ru(CO) sub(3)Cl sub(2)] sub(2) in molten naphthalene at 250 [degrees]C provides facile access to the first all-second-row transition metal heterometallic chain compound, MoMoRu(dpa) sub(4)Cl sub(2) (1). The one-electron oxidized compound [MoMoRu(dpa) sub(4)Cl sub(2)](OTf ) (2) is synthesized by reaction of 1 with FeCp sub(2)(OTf). X-ray crystallography reveals a contraction of the Mo-Ru bond distance from 2.38 [Angstrom] in 1 to 2.30 [Angstrom] in 2, and an elongation of the Mo-Mo bond distance from 2.12 [Angstrom] in 1 to 2.21 [Angstrom] in 2. The short Mo-Ru bond distances indicate significant electron delocalization along the Mo-Mo-Ru chain, which is quantified by density functional theory (DFT) calculations. Molecular orbital analyses of both compounds based on DFT results reveal full delocalization of the orbitals of [sigma] and [pi] symmetry for both compounds. Additionally, delta orbital delocalization is observed in 2.