Coordination trimeric

Among the carboxylates, scandium formate has a 2-D polymeric structure, whilst in the acetate, chains of 8c + ions are bridged by acetate groups (Pigure 3) with essentially octahedral coordination of scandium. 8imilar bridging is found in the chloroacetate, where the six-coordination is in contrast with the nine-coordinate trimeric structure adopted by the heavier lanthanide ions. 8candium propynoate has... 

In 1961, Cotton and Fadder 43) further found that Ni(acac)2 exists in a monomer-trimer equilibrium in diphenylmethane over a 80—200 °C range. At low temperatures the green octahedrally coordinated trimeric species predominates, but at 200 °C the monomeric, square planar nickel complex is stable giving a red solution. Other /9-diketonate-nickel(II) complexes found to participate in a monomeric-trimer equilibrium from spectral and magnetic studies were... 

The less branched, more associated tetraalkyl titanates are more slowly hydroly2ed because titanium is more fully coordinated. The hydrolysis of tetraethyl titanate has also been considered ia terms of its trimeric form ... 

Orthorhombic HBO2 consists of trimeric units B303(0H)3 which are linked into layers by H bonding (Fig. 6.26) all the B atoms are 3-coordinate. Monoclinic HBO2 is built of chains of composition [B304(0H)(H20)] in which some of the B atoms are now 4-coordinate, whereas cubic HBO2 has a framework structure of tetrahedral BO4 groups some of which are H bonded. The increase in CN of B is paralleled by an increase in density and mp. 

LCo(H20)6] ion, and bidentate /V-donor ligands such as cn, bipy and phen form octahedral cationic complexes [Co(L-L)3] , which are much more stable to oxidation than is the hexaammine [Co(NH3)6l . Acac yields the orange [Co(acac)2(H20)2] which has the tram octahedral structure and can be dehydrated to [Co(acac)2l which attains octahedral coordination by forming the tetrameric species shown in Fig. 26.3. This is comparable with the trimeric [Ni(acac>2]3 (p. 1157), like which it shows evidence of weak ferromagnetic interactions at very low temperatures. fCo(edta)(H20)] is ostensibly analogous to the 7-coordinate Mn and complexes with the same stoichiometry, but in fact the cobalt is only 6-coordinate, 1 of the oxygen atoms of the cdta being too far away from the cobalt (272 compared to 223 pm for the other edta donor atoms) to be considered as coordinated. 

Monomer-oligomer equilibria. [Ni(Me-sal)2], mentioned above as a typical planar complex, is a much studied compound. In pyridine it is converted to the octahedral bispyridine adduct (/zsoo = 3.1 BM), while in chloroform or benzene the value of is intermediate but increases with concentration. This is ascribed to an equilibrium between the diamagnetic monomer and a paramagnetic dimer, which must involve a coordination number of the nickel of at least 5 a similar explanation is acceptable also for the paramagnetism of the solid when heated above 180°C. The trimerization of Ni(acac)2 to attain octahedral coordination has already been referred to but it may also be noted that it is reported to be monomeric and planar in dilute chloroform solutions. 

Figure 27-10 Anhydrous acetates of Pd" and Pt" (a) trimeric [Pd(02CMe)2h involving square-planar coordinated Pd but no metal-metal bonding (average Pd -Pd = 315pm), and (b) tetrameric [Pt(02CMc)2]4 involving octahedrally coordinated Pt and metal-metal bonds (average Pt-Pi = 249.5 pm). llie four bridging ligands in the Pt,j plane are much more labile than the others.

Other isomers of cdt are also obtained and, if a coordination site on the nickel is blocked by the addition of a ligand such as a tertiary phosphine, dimerization of the butadiene, rather than trimerization, occurs. 

Polymerization of alkynes by Ni" complexes produces a variety of products which depend on conditions and especially on the particular nickel complex used. If, for instance, O-donor ligands such as acetylacetone or salicaldehyde are employed in a solvent such as tetrahydrofuran or dioxan, 4 coordination sites are available and cyclotetramerization occurs to give mainly cyclo-octatetraene (cot). If a less-labile ligand such as PPhj is incorporated, the coordination sites required for tetramerization are not available and cyclic trimerization to benzene predominates (Fig. A). These syntheses are amenable to extensive variation and adaptation. Substituted ring systems can be obtained from the appropriately substituted alkynes while linear polymers can also be produced. 

A second, red form has recently been reported from mass spectral evidence, it may be a trimer. In the gas phase at 120°C, it consists mainly of a trimer (with octahedrally coordinated Ru) [18],... 

It is an intensely reactive and hygoscopic yellow-brown substance (m.p. 75-78°C) its volatility suggests a low molecular mass Mossbauer spectra indicate 6-coordinate gold while the Raman spectrum is interpreted in terms of cw-bridged octahedral units. In the gas phase at 170°C, it comprises dimers and trimers [29] (electron diffraction). 

An X-ray crystal-structure determination (370) revealed that mixed, nickel coordination exists in the trimeric complex, [Ni(S2CPh)2]3. The trimeric structure is similar to that found (371) in [Pd(PhCS2>]. The structure contains one molecule of type A linked centrosymmetrically through short Ni-S bridges to two molecules of type B, the three molecules being closely parallel (XXVII). Bonamico and co-workers (372)... 

All mechanisms proposed in Scheme 7 start from the common hypotheses that the coordinatively unsaturated Cr(II) site initially adsorbs one, two, or three ethylene molecules via a coordinative d-7r bond (left column in Scheme 7). Supporting considerations about the possibility of coordinating up to three ethylene molecules come from Zecchina et al. [118], who recently showed that Cr(II) is able to adsorb and trimerize acetylene, giving benzene. Concerning the oxidation state of the active chromium sites, it is important to notice that, although the Cr(II) form of the catalyst can be considered as active , in all the proposed reactions the metal formally becomes Cr(IV) as it is converted into the active site. These hypotheses are supported by studies of the interaction of molecular transition metal complexes with ethylene [119,120]. Groppo et al. [66] have recently reported that the XANES feature at 5996 eV typical of Cr(II) species is progressively eroded upon in situ ethylene polymerization. 

The reactivity of three-coordinate [BpBut]ZnR is summarized in Scheme 12. The Zn-C bonds of [BpBut]ZnR are readily cleaved by H20 and MeC02H to give the hydroxo and acetato complexes [BpBut]Zn(/i-OH) 3 and [BpBut]Zn(7j2-02CMe), respectively. The structure of [BpBut]Zn(/u-OH) 3, determined by x-ray diffraction, is a cyclic trimer, with Zn-OH bond lengths in the range 1.89-1.99 A (Fig. 29). The... 

To substitute the strongly bound axial CO ligand of the ruthenium or osmium center, it is necessary to employ more drastic conditions than simple stirring at room temperature. Imamura (11,20) used photolysis to synthesize porphyrin trimers on the basis of simultaneous coordination of two 4-pyridyl porphyrins to the same ruthenium porphyrin (12, Fig. 3). Some interesting photophysical behavior was observed for these systems. The trimers have an extra UV-Vis absorption band at about 450 nm which is ascribed to metal-ligand charge transfer (MLCT), a d7r(Ru(II))-7r (OEP) transition. This band shows a batho-chromic shift in more polar solvents, and decreased in intensity when... 

Fig. 3. A trivial closed trimer assembled on a six-coordinate metalloporphyrin.

Sanders (14) has exploited the strong and selective coordination of phosphine donor groups to Ru(II) to construct hetero-dimetallic porphyrin dimers (17, Fig. 5). An alkyne-phosphine moiety introduced on the periphery of a free base or metalloporphyrin (M = Zn or Ni) spontaneously coordinates to a Ru(II)(CO) porphyrin when the two porphyrins are mixed in a 1 1 ratio. Coordination is characterized by a downfield shift of the 31P resonance (A<531P = 19 ppm). There is no evidence of self-coordination of the zinc porphyrin at 10 6 m in toluene, there is no shift in the Soret band in the UV-Vis absorption spectrum. The Ni-Ru dimer was observed by MALDI-TOF mass spectrometry. Heating the Ru(II)CO porphyrin with 2 equivalents of the phosphine porphyrins led to quantitative formation of trimeric assemblies. 

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