Organometallic Selenolates. 5.¹ Synthesis and Complexing Properties of 2-Propene- and 2-Methyl-2-propeneselenolato Molybdenum and Tungsten Compounds. Crystal Structures of cp(CO)₃WSeCH₂C(CH₃)CH₂, [cp(CO)₂MoSeCH₂C(CH₃)CH₂]₂, [cp(CO)₃Mo(μ-SeCH₂C(CH₃)CH₂)W(CO)₅], [cp(CO)₃Mo(μ-SeCH₂C(CH₃)CH₂)Mo(CO)_5<

Abstract

2-Propene- and 2-methyl-2-propeneselenolato complexes of molybdenum(II) and tungsten(II) have been prepared via insertion of gray selenium into alkali-metal-molybdenum and -tungsten bonds and subsequent reaction with allyl and beta-methallyl chlorides. The complexes are monomeric in the solid state. The (beta-methallyl)molybdenum compound cp(CO)(3)MoSeCH(2)C(CH(3))=CH(2) (2) decomposes slowly in solution with CO loss and formation of the corresponding dimer [cp(CO)(2)MoSeCH(2)C(CH(3))=CH(2)](2) (3), whose crystal structure has been determined (C(22)H(24)Mo(2)O(4)Se(2), monoclinic, P2(1)/c, a = 11.151(2) Å, b = 13.436(3) Å, c = 16.872(3) Å, beta = 102.42(2) degrees, Z = 4). A monomeric structure has been found for cp(CO)(3)WSeCH(2)C(CH(3))=CH(2) (5) (C(12)H(12)O(3)SeW, triclinic, P&onemacr;, a = 7.592(3) Å, b = 7.700(3) Å, c = 12.296(5) Å, alpha = 98.31(4) degrees, beta = 104.24(2) degrees, gamma = 108.49(3) degrees, Z = 2). Additionally, the complexing properties of the selenolato complexes have been investigated. The reactions of the molybdenum complexes cp(CO)(3)MoSeCH(2)CH=CH(2) (1) and (2) with the metal(0)-carbonyl complexes W(CO)(5)(THF), (CH(3)CN)(3)Mo(CO)(3), and (eta(6)-C(7)H(8))Mo(CO)(3) (C(7)H(8) = cycloheptatriene) led to the formation of [cp(CO)(3)Mo(&mgr;-SeCH(2)C(CH(3))=CH(2))M(CO)(5)] (M = W (6), Mo (7)) and [cp(CO)(3)Mo(&mgr;-SeCH(2)CH=CH(2))Mo(CO)(5)] (8), respectively. 6 and 7 are isostructural and crystallize in the monoclinic space group P2(1)/n (6, C(17)H(12)MoO(8)SeW, a = 14.708(2) Å, b = 9.837(2) Å, c = 14.958(2) Å, beta = 103.030(10) degrees, Z = 4; 7, C(17)H(12)Mo(2)O(8)Se, a = 14.712(2) Å, b = 9.8670(10) Å, c = 14.982(2) Å, beta = 103.100(10) degrees, Z = 4), whereas [cp(CO)(3)Mo(&mgr;-SeCH(2)CH=CH(2))Mo(CO)(5)] (8) crystallizes in the noncentrosymmetric orthorhombic space group Pna2(1) (C(16)H(10)Mo(2)O(8)Se, a = 18.638(4) Å, b = 9.707(2) Å, c = 11.169(3) Å, Z = 4). Furthermore, (77)Se-NMR spectra displayed chemical shifts consistent with earlier results on related complexes.