STAR-SHAPED TRICARBONYL(CYCLOBUTADIENE)IRON AND CYMANTRENE COMPLEXES - BUILDING-BLOCKS FOR CARBON NETS AND ORGANOMETALLIC CONSTRUCTION SETS

(C4I4)Fe(CO)3 (2) and (C5I5)Mn(CO)3 (3) react with a variety of stannylbutadiynes (9) to form the corresponding [C4(C=CC=CR)4]Fe(CO)3 (10) and [C5(C=CC=CR)5]Mn(CO)3 (11) (R = pentyl, tert-butyl, isopropyl, trimethylsilyl) complexes. Iodide 2 coupled to a hexatriyne derivative to yield 13. Pentametallic X-shaped complexes (16) are obtained by Pd-catalyzed coupling of organometallic stannylacetylenes with 2 in one step. X-ray crystal structure analyses have been carried out on several of the cross-shaped complexes obtained. It is likely that these molecules can also be useful in the synthesis of larger nanometer-scale objects. Crystal structures have been carried out for compounds 10a (P1BAR; a = 15.3172(9) angstrom, b = 12.331(1) angstrom, c = 11.705(2) angstrom; alpha = 97.585(8)-degrees, beta = 95.463(7)-degrees, gamma = 91.232(6)-degrees; V = 2180.2 angstrom3; Z = 2; R = 3.8%, R(w) = 3.8% for 3194 reflections with F > 3sigma(F)), 13 (P1BAR; a = 11.7599(9) angstrom, b = 9.186(3) angstrom, c = 20.055(2) angstrom; alpha = 99.850(16)-degrees, beta = 85.556(7)-degrees, gamma = 104.040(13)-degrees; V = 2069.2 angstrom3; Z = 2; R = 3.9%, R(w) = 4.2% for 3239 reflections with F > 3sigma(F)), 16a (P1BAR; a = 13.0355(15) angstrom, b = 13.043(3) angstrom, c = 13.128(2) angstrom; alpha = 85.4678(15)-degrees, beta = 80.566(9)-degrees, gamma = 71.034(13)-degrees; V = 2081.5 angstrom3; Z = 2; R = 3.4%, R(w) = 3.6% for 3095 reflections with F > 3sigma(F)), and 16b (P1BAR; a = 12.269(3) angstrom, b = 16.298(3) angstrom, c = 11.560(3) angstrom; alpha = 99.089(9)-degrees, beta = 108.907(10)-degrees, gamma = 91.776(10)-degrees; V = 2158.5 angstrom3; Z = 2; R = 5.0%, R(w) = 5.4% for 4195 reflections with F > 3sigma(F)).