The ligation properties of three new upper-rim-substituted calix[4]arene ligands, 5,17-bis(hydroxymethyl)-tetra-n-butoxycalix-[4]arene ((HOCH2)(2)-(n)Bu(4)Clx, 7), 5,17-bis((diphenylphosphinito)methoxy)-tetra-n-butoxycalix[4]arene ((PPh2OCH2)(2)-(n)Bu(4)Clx, 8), and 5,17-bis((diphenylphosphino)methyl)-tetra-n-butoxycalix[4]arene ((PPh2CH2)(2)-(n)Bu(4)Clx, 10) are reported herein. The newly prepared compounds differ from previously reported diametrically substituted calix[4]arene derivatives in that the lower-rim substituent was n-butyl. The presence of this lower-rim substituent did not reduce the inherent crystallinity of these complexes as purification of all materials occurred via simple crystallizations. The key precursor for the syntheses of 8 and 10 was 7, acquisition of which occurred in six steps starting from tetra-tert-butylcalix[4]arene, 1. Calix[4]arene derivatives include, tetra-n-butoxycalix[4]arene ((n)Bu(4)Clx, 3), 5,11,17,23-tetrabromo-tetra-n-butoxycalix[4]arene (Br-4-(n)Bu(4)Clx, 4), 5,17-dibromo-tetra-n-butoxycalix[4]arene (Br-2-(n)Bu(4)Clx, 5), 5,17-bis(formyl)-tetra-n-butoxycalix[4]arene ((CHO)(2)-(n)Bu(4)Clx, 6), and 5,17-bis(chloromethyl)-tetra-n-butoxycalix[4]arene ((CICH2)(2)-(n)Bu(4)Clx, 9), all of which were synthesized using modifications of existing procedures. Characterization of all compounds occurred, when possible, using H-1, C-13, and P-31 NMR, elemental analyses, FAB-MS, ESI-MS, FT-IR, and X-ray crystallography. The solid-state structures of all calix[4]arene intermediates and ligands showed that the annulus adopted the pinched-cone conformation in which the average C(5)C-. . .(17) intraannular separation was 4.5 +/- 0.4 Angstrom. Reaction of 7 with CpTiMe3 yielded the cis-chelate, CpTi(Me)[(OCH2)(2)-(n)Bu(4)Clx] (11), quantitatively. Data obtained using ESI-MS (positive-ion mode) confirmed the monomer formulation showed above, and 1H NMR spectra provided sufficient information to deduce the nature of the Ti coordination sphere. Reaction of 8 with Cis-CI2Pd(NCPh)(2) in refluxing benzene afforded cis-Cl2Pd[(PPh2OCH2)(2)-(n)Bu(4)Clx] (2) in good yields. The monomeric identity of this compound was verified by both X-ray crystallography and positive-ion ESI-MS. The cis-bidentate calix[4]arene ligand did not undergo any noticeable contortion upon chelation of the PdCl2 fragment. Acid-promoted decomposition of 12 occurred in the presence of adventitious HCI and gaseous HCI, and the products of this decomposition were 9 and [mu(2)-ClPd(PPh2OH)(PPh2O)](2). In addition, chelates of 8 that contained Mo(CO)(3)L (L = NCMe (14a), NCEt (14b), and CO (14c)) showed that the mode of coordination was relatively insensitive to the identity of the metal. X-ray crystallography afforded views of the solid-state structures of 14b,c and, like 12, showed that the Mo(CO)3L fragment resided above the pinched-cone of the calix[4]arene. H-1 NMR revealed that C-H/pi interactions existed between L (14a,b) and a phenyl ring of the coordinated phosphinite. Finally, the bis(diphenylphosphine)calix[4]arene ligand (10) readily coordinated the Mo(CO)(3)L species, but the reaction did not go to completion, as evidenced by H-1 NMR, even after a 5 day reaction time. Data suggest that the product is similar to that observed for 12 and 14, but the incomplete reaction complicated attempts to obtain pure material and prohibited definitive assignment of the coordination array.