SYNTHESES AND STRUCTURES OF THE PHENYLBISMUTH TRANSITION-METAL CARBONYL-COMPOUNDS [PPN][PH2BIFE(CO)4], (PH2BI)2FE(CO)4, [PHBIFE(CO)4]2, AND PH2BIMN(CO)5

Treatment of Na2Fe(CO)4 with 1 equiv of Ph2BiCl in tetrahydrofuran (THF) affords Na[Ph2BiFe(CO)4], characterized as the [PPN]+ (PPN = bis(triphenylphosphine)nitrogen(1+)) salt ([PPN][I]); adding a second 1 equiv of Ph2BiCl produces (Ph2Bi)2Fe(CO)4 (II), which decomposes to [PhBiFe(CO)4]2 (III) in solution. III is also obtained in poor yield from the reaction of PhBiBr2 and Na2Fe(CO)4.3/2diox (diox = dioxane) in THF. The reduction of Ph2BiCl with 2 equiv of sodium in liquid NH3 followed by addition of Fe(CO)5 yields II and III along with traces of Ph4Bi2. I, II, and III.CH2Cl2 have been characterized by single-crystal X-ray diffraction. Crystals of [PPN][I] are monoclinic, Cc (No. 9), with a = 13.08 (1) angstrom, b = 15.832 (9) angstrom, c = 23.18 (1) angstrom, beta = 99.53 (6)-degrees, V = 4733 (6) angstrom-3, and Z = 4. Convergence was achieved with R = 5.8% and R(w) = 6.0% for 2584 observed reflections. The iron atom has a trigonal-bipyramidal coordination geometry with the pyramidal Ph2Bi group occupying an axial position. The Bi-Fe distance is 2.676 (4) angstrom. II crystallizes in the monoclinic space group P2(1)/n (No. 14) with a = 12.009 (3) angstrom, b = 13.074 (2) angstrom, c = 17.264 (2) angstrom, beta = 96.78 (1)-degrees, V = 2691.5 (8) angstrom-3, and Z = 4. The structure was refined to R = 5.0% and R(w) = 5.8% for 3698 observed reflections. The octahedral Fe(CO)4 group in II is bonded to two Ph2Bi groups in cis positions. The average Bi-Fe distance in this compound is 2.828 (6) angstrom. III.CH2Cl2 crystallizes in the monoclinic crystal system, space group C2/c (No. 15) with a = 17.681 (6) angstrom, b = 7.069 (2) angstrom, c = 21.573 (10) angstrom, beta = 101.19 (3)-degrees, V = 2645 (2) angstrom-3, and Z = 4. The structure was refined to R = 4.2% and R(w) = 4.9% for 1821 reflections with I > 3-sigma(I). The structure consists of a Bi2Fe2 planar parallelogram situated about an inversion center with an average Bi-Fe distance of 2.786 (3) angstrom. Each bismuth atom is bonded to one phenyl group. The iron carbonyl groups exhibit cis-pseudooctahedral coordination environments. The reaction of Ph2BiX (X = Cl, I) with Na[Mn(CO)5] produces octahedral Ph2BiMn(CO)5 (IV), which crystallizes in the triclinic space group P1BAR (No. 2) with a = 10.135 (4) angstrom, b = 13.484 (4) angstrom, c = 6.567 (4) angstrom, alpha = 99.11 (3)-degrees, beta = 92.53 (4)-degrees, gamma = 86.46 (2)-degrees, V = 883.9 (6) angstrom-3, Z = 2, R = 4.4%, and R(w) = 5.6% for 2036 observed reflections. The Bi-Mn distance is 2.842 (2) angstrom.