A synthetic approach to a two-dimensional grid polymer is proposed and the execution of initial steps is described. Pd-catalyzed coupling of (1,12-dicarba-closo-dodecaboran-1-yl)copper ( 10) with iodobenzene, mdiiodobenzene, and 1,3,5-triiodobenzene yielded the known 1,12-dicarba-closo-dodecaboran-1-ylbenzene (3) and the new m-bis(1,12-dicarba-closo-dodecaboran-1-yl)benzene (4) and 1,3,5-tris(1,12-dicarba-closo-dodecaboran-1yl)benzene (1), respectively. Each arm of the trigonal connector 1 was provided with one or two sticky tentacles by conversion to 1,3,5-tris [12-((3-(ethylthio)propyl)dimethylsilyl)-1,12-dicarba-closo-dodecaboran-1-yl]benzene (7) and 1,3,5-tris [12-(bis(3-(ethylthio)propyl)methylsilyl)-1,12-dicarba-closo-dodecaboran-1-yl]benzene (8). Linear coupling of carboranyl CH terminals through a mercury atom produced very stable dimeric structures from 3 and 4. The carborane 3, its mercury-linked dimer 13, the 1:1 complex of 13 with 2,2′-bipyridyl, and the 2:1 complex of 13 with 2,2′-bipyrimidyl have been structurally characterized by single-crystal X-ray crystallography, but crystals of 1 showed an intriguing disorder and could not be used for molecular structure determination. Grazing incidence IR spectra show that the tentacled species 7 and 8 adsorb firmly on the surface of gold, apparently without a strong preference for a particular orientation. At room temperature, the tritentacled species 7 can be removed readily and the hexatentacled species 8 more slowly by treatment with a THF solution containing fluoride, which severs the tentacles.

We report the synthesis of (cyclobutadiene)cyclopentadienylcobalt derivatives, C4R4−Co−C5Y5, where R is a rigid arm capable of linear coupling through its para position and the tentacle Y carries a functionality with a large affinity for the surface of mercury. The compounds are needed for a proposed synthesis of a square-grid polymer by 2-dimensional cross-linking polymerization, which calls for cross-shaped star connector modules mounted horizontally on a flat pedestal with a large affinity to a liquid interface. The substituents are R = 4-pyridyl, 4-iodophenyl, 4-bromophenyl, 4-(ethoxycarbonyl)phenyl, 4-(1,12-dicarba-closo-dodecaboran-1-yl)phenyl, 4-carboxyphenyl, 4−[(triethylsilyl)ethynyl]phenyl, Y = H; R = phenyl, Y = (trifluoroacetoxy)mercurio, iodo; R = 4-bromophenyl, Y = (trifluoroacetoxy)mercurio; R = 4-(ethoxycarbonyl)phenyl, Y = [(2-hydroxyethyl)thio]mercurio. Single-crystal X-ray diffraction structures are reported for R = 4-pyridyl, 4-(1,12-dicarba-closo-dodecaboran-1-yl)−phenyl, 4-(ethoxycarbonyl)phenyl with Y = H, R = phenyl with Y = (trifluoroacetoxy)mercurio, and bis[4-(1,12-dicarba-closo-dodecaboran-1-yl)phenyl]acetylene and phenyl[4−(1,12-dicarba-closo-dodecaboran-1-yl)phenyl]acetylene.

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LiR' or MgR'X), i.e. wherein one or two Cu centers are replaced by Li or MgX. The trinuclear unit has a reactive site to which we anticipate that the alkene function of enones would coordinate, i.e. the initial reaction step proposed for their copper (1)-catalyzed reaction with organometallic reagents.'3*22~23 This coordination does not occur in [Cu3(SC6H,(CH(R)NMe,)-2~,(C~-~-Bu)] since the strength of the side-on alkynyl to copper bond favors a hexanuclear structure. However, with phosphines as two-electron donors, trinuclear compounds [Cu3{ SC6H4-(CH(R)NM~,)-~),(C=~-~-BU)(P(OM~)~))] are formed. Four fluxional processes in hexanuclear and trinuclear alkynylcopper arenethiolah have been observed. In order (22) (a) Ullenius, C.; Christenson, B. Knotter, D. M.; Janssen, M. D.; Van Klaveren, M.; Boersma, J.; Van Koten, G. Tetrahedron: Asymmetry 1991, 2, 1097.

The di-p-carboxylato complexes [{Pd(CH,C,H,N) (p-O,CR)},] (CH,C,H,N = 8-quinolylmethyl, R = Me or CF,) react in methanol with NaOH(aq) (1 :1 molar ratio) to give the corresponding mixed hydroxocarboxylato-bridged complexes [{Pd(CH,C,H,N)},(p-OH) (p-O,CR)] ( R = Me 1 or CF, 2). The reactions of 1 or 2 with arylamines or thiols (1 : 1 molar ratio) yielded the corresponding amido-or thiolato-carboxylato complexes [{Pd(CH,C,H,N)},(p-0,CMe) (p-NHR)] (R = Ph 3, p-MeC,H, 4 or p-NO,C,H, 5) or [{Pd(CH,C,H,N)},(p-O,CR)(p-SR')] (R = Me, R' = Et 6, But 7 , Ph 8 or p-MeC,H, 9; R = CF,, R' = But 10). The 'H NMR data indicate a cis arrangement of the CH,C,H,N ligands. The crystal structure of complex 10 has been determined. It confirms the cis relationship of the CH, C, H, N ligands. The co-ordination at each palladium atom is approximately square planar and the oxygen atoms of the trifluoroacetate ligands are trans to carbon. The Pd,(p-OCOCF,) (p-SBu') core is quite bent with an angle of 55" between the two palladium co-ordination planes.