We have been studying chemical processes that use discrete molecular reagents to form extended solid inorganic materials. The goals of this program have been to determine how best to design and implement these molecular precursor reactions and to discover what chemical intermediates lie on the molecules-to-solids paths. In this manuscript we report studies of the reactions of the low-valent iron complex Fe(C8H8)2 with low-valent tellurium compounds of the form TePR3 (R = various hydrocarbon groups) that lead ultimately to the exclusively inorganic extended solid compounds Fe(x)Te(y). We have found four Fe/Te cluster types that are chemical intermediates in this process : Fe4Te4(PEt3)4,1;Fe4Te4(PiPr3)4,2;Fe6Te8(PMe3)6,3;(dmpe)2FeTe2,4;(depe)2FeTe2,5;Fe4Te6(dmpe)4,6. (Here (i)Pr = CHMe2, dmpe = Me2PCH2CH2PMe2, and depe = Et2PCH2CH2PEt2.) The different clusters form when different supporting phosphine ligands are employed. We report the syntheses, structures, and properties of these intermediates and the comparisons and contrasts between these molecular intermediates and the extended solid products. We note that when larger ligands are used smaller clusters are formed. We also note what features of the molecular structures lead to ferromagnetic versus antiferromagnetic coupling of the distinct Fe centers. We have determined the structures of the following materials crystallographically : 2 (C36Hg4Fe4Te4P4; tetragonal, P421cBAR; a = 14.0469(7) angstrom, c = 13.5418(9) angstrom; z = 2); 3 (C18H54Fe6TeBP6; trigonal, R3BAR; a = 11.859(2) angstrom, c = 26.994(5) angstrom; Z = 3); dmpe.2Te (C6Hl6Te2P2; monoclinic, P2(1)/c; a = 6.0890(4) angstrom, b = 10.7934(7) angstrom, c = 9.8200(5) angstrom, beta = 104.63(7)-degrees; Z = 2); 5 (C20H48FeTe2P4; orthorhombic, Pbnn; a = 10.997(3) angstrom, b = 14.157(3) angstrom, c = 18.345(4) angstrom; Z = 4); 6 (C24H64Fe4Te6P8; orthorhombic, Abaa; a = 12.056(3) angstrom, b = 17.725(5) angstrom, c = 21.403(8) angstrom; Z = 4).