Synthesis, x-ray crystal structure determination, and NMR spectroscopic investigation of two homoleptic four-coordinate lanthanide complexes: Trivalent ({sup t}Bu{sub 2}P){sub 2}La[({mu}-P{sup t}Bu{sub 2}){sub 2}Li(thf)] and divalent Yb[({mu}-P{sup t}Bu{sub 2}){sub 2}Li(thf)]{sub 2}
- Universitaet Muenchen, Garching (Germany)
La(OSO{sub 2}CF{sub 3}){sub 3} reacts with 4 equiv of LiP{sup t}Bu{sub 2} in tetrahydrofuran to give dark red ({sup t}Bu{sub 2}P){sub 2}La[({mu}-P{sup t}Bu{sub 2}){sub 2}Li(thf)] (1). Yb(OSO{sub 2}CF{sub 3}){sub 3} reacts with LiP{sup t}Bu{sub 2} in tetrahydrofuran in a 1:5 ratio to produce Yb[({mu}-P{sup t}Bu{sub 2}){sub 2}Li(thf)]{sub 2} (2) and {1/2} an equiv of {sup t}Bu{sub 2}P-P{sup t}Bu{sub 2}. Both 1 and 2 crystallize in the monoclinic space group P2/c. Crystal data for 1 at 214 K; a = 11.562 (1) {angstrom}, b = 15.914 (1) {angstrom}, c = 25.373 (3) {angstrom}, {beta} = 92.40(1){degrees}; V = 4664.5 {angstrom}{sup 3}; Z = 4; D{sub calcd} = 1.137 g cm{sup -3}; R{sub F} = 2.61%. Crystal data for 2 at 217 K: a = 21.641 (2) {angstrom}, b = 12.189 (1) {angstrom}, c = 20.485 (2) {angstrom}, {beta} = 109.01 (1){degrees}; V = 5108.9 {angstrom}{sup 3}; Z = 4; D{sub calcd} = 1.185 g cm{sup -3}; R{sub F} = 2.80%. The molecular structures of 1 and 2 show the four-coordinate lanthanide atoms in distorted tetrahedral environments. These complexes are the first representatives of the lanthanide elements surrounded by four only-phosphorus-containing substituents. The main features of the crystal structure of 1 are the shortest La-P distances (2.857(1) and 2.861(1) {angstrom}) reported so far and a three-coordinate lithium cation. The molecular structure of 2 represents a divalent bis {open_quotes}ate{close_quotes} complex with two three-coordinate lithium cations. Complex 2 shows photoluminescent properties. VT NMR spectra ({sup 7}Li and {sup 31}P) are reported for 1 and 2.
- OSTI ID:
- 255626
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 1 Vol. 35; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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