Syntheses and crystal structures of new naphthalene- and anthracene-vanadate salts and an unprecedented dimetallabis(anthracene) sandwich complex: [Na(tetrahydrofuran) 3 ][V 2 (anthracene) 2 ].

Reduction of bis(naphthalene)vanadium(0) by potassium naphthalene (KNp) in tetrahydrofuran (THF) provides a highly reactive, thermolabile, and so far unisolable brown substance, which affords the first reported derivatives of bis(naphthalene)vanadates. From these solutions, thermally stable (298 K) and structurally characterized compounds have been obtained, including dark-red rods of catena-poly[bis(μ 3 -η 4 :η 6 :η 4 -naphthalene)tetrakis(tetrahydrofuran)dipotassiumvanadium], [K 2 V(C 4 H 8 O) 4 (C 10 H 8 ) 2 ] n or [K(THF) 2 ] 2 [V(C 10 H 8 ) 2 ] (3), and red plates of (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane)potassium [1,2-bis(dimethylphosphanyl)ethane]bis(η 4 -naphthalene)vanadium tetrahydrofuran monosolvate, [K(C 18 H 36 N 2 O 6 )][V(C 10 H 8 ) 2 (C 6 H 16 P 2 )]·C 4 H 8 O or [K([2.2.2]cryptand)][V(C 10 H 8 ) 2 (dmpe)]·THF [dmpe is 1,2-bis(dimethylphosphanyl)ethane] (4b). Notably, [V(C 10 H 8 ) 2 ] 2- is the only example of a structurally authenticated homoleptic bis(arene)metallate dianion and was obtained by further reduction of the brown material by KNp in THF, in the presence of trimethylphosphane (PMe 3 ). Addition of anthracene (An) to the brown material in THF afforded deep-violet and paramagnetic crystalline (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium [(η 4 -anthracene)(tetrahydrofuran)vanadium]-μ-η 4 :η 2 -anthracene-[(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium]-μ-η 2 :η 4 -anthracene-[(η 4 -anthracene)(tetrahydrofuran)vanadium] tetrahydrofuran disolvate, [K(C 12 H 24 O 6 )(C 4 H 8 O) 2 ][KV 2 (C 12 H 24 O 6 )(C 4 H 8 O) 2 (C 14 H 10 ) 4 ]·2C 4 H 8 O or [K(18-crown-6)][K(18-crown-6)(THF) 2 ][V(C 14 H 10 ) 2 (THF)] 2 ·2(THF) (5), which readily reacted with PMe 3 and dmpe to give new vanadate salts. These were structurally characterized as (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium bis(η 4 -anthracene)(trimethylphosphane)vanadium tetrahydrofuran monosolvate, [K(C 12 H 24 O 6 )(C 4 H 8 O) 2 ][V(C 14 H 10 ) 2 (C 3 H 9 P)]·C 4 H 8 O or [K(18-crown-6)(THF) 2 ][V(C 14 H 10 ) 2 (PMe 3 )]·THF (6), and tetrakis(1,2-dimethoxyethane)potassium bis(η 4 -anthracene)[1,2-bis(dimethylphosphanyl)ethane]vanadium, [K(C 4 H 10 O 2 ) 4 ][V(C 14 H 10 ) 2 (C 6 H 16 P 2 )] or [K(DME) 4 ][V(C 14 H 10 ) 2 (dmpe)] (DME is 1,2-dimethoxyethane) (7b). The last three structures contain the first known bis(anthracene)vanadates and are thereby derivatives of the unknown bis(anthracene)vanadium(0). Attempts to obtain the sodium salt analog of 5 in THF resulted instead in the formation of a unique substance, (μ 3 -η 6 :η 6 :η 6 -anthracene)(μ 2 -η 6 :η 6 -anthracene)tris(tetrahydrofuran)sodiumdivanadium, [NaV 2 (C 14 H 10 ) 2 (C 4 H 8 O) 3 ] or [Na(THF) 3 ][V 2 (C 14 H 10 ) 2 ] (8), containing the first reported dimetallabis(anthracene) sandwich compound.