Two-way synthesis of a double-lantern heterobimetallic complex [Pd(μ-OOCMe)4Co]2(μ-OOCMe)2Pd(py)2

Structure of reaction products of hydrous and anhydrous zinc acetates with 1,10-phenanthroline

“…The simplest mononuclear transition metal car boxylates can be used as unit building blocks for com plex molecules and clusters, in particular heterometal lic ones [1,2]. One method for preparing such the compounds is reacting bi or polynuclear carboxylates with strong N ,O donor molecules [3][4][5].…”

Paramagnetic Metal–Metal Bonded Heterometallic Complexes

“…To support the two metals, research groups have focused on providing either a 3-fold symmetric or a 4-fold symmetric coordination environment. The groups of Lu and Thomas have both utilized 3-fold symmetric ligand scaffolds to support a variety of unique heterobimetallic species. − Some of these species have found success in catalytic transformations and small molecule activation, ,,,,, cross-coupling reactions, ,,, and C–H activation. , Detailed description of their reactivity is described elsewhere. ,, In addition to these 3-fold symmetric species, the groups of Vargaftik, Doerrer, Zamora, and Berry have synthesized heterobimetallic compounds supported by four ligands in a paddlewheel arrangement, affording structures with C 4 symmetry. − Remarkably, the compounds comprising this section display a wide range of magnetic behavior, sometimes counterintuitive and surprising.…”

“…Heterobimetallic compounds with C 4 symmetry were reported first, following the earlier work of Lippert, Kinoshita, and Matsumoto described in section . Vargaftik and co-workers found in 2005 that carboxylate ligands could be used to support heterobimetallic compounds having Pd–M (M = Mn, Co, Ni, Cu), − and later Pt–Co, cores. Doerrer and co-workers have reported a suite of Pt–M compounds (M = Fe, Co, Ni) supported by thiocarboxylate ligands. − Berry and co-workers recently reported a Pd–Fe complex supported by mercaptopyridine ligands …”

“…Both Doerrer and Berry laboratories have taken advantage of similar HSAB principles to form C 4 symmetric compounds using the ligands shown in Figure . The Doerrer and Zamora groups have used thiocarboxylate ligands tba and SAc, while the Berry group has used 2-thiopyridone (PyS). ,,− , Interestingly, Vargaftik and co-workers have shown conclusively that HSAB ligand design is not absolutely necessary to support heterobimetallic compounds containing Pd or Pt–their group has utilized the simple acetate ligand. − …”

Competition between 3d metals(II) and palladium(II) in the reaction of heterobimetallic complexes Pd(μ-OOCMe)4M(OH2) (M=Ni, Co, Mn) with azobenzene

“…However, the tetraacetate bridging system is rather strong (providing a very short, $2.5 Å, Pd-M distance and difficult accessibility of Pd II atom), whereas the axial position of the co-metal coordination sphere is rather labile and easy accessible to a nucleophilic attack. Earlier, we found that such N-donors as 1,10-phenanthroline and 2,2 0 -bipyridine attach to a co-metal rather than to palladium atom, keeping almost intact the acetate bridging system [5], whereas pyridine partially decomposes the heterometallic complex to form the pentanuclear bis-paddlewheel compound [Pd(l-OOCMe) 4 Co] 2 (lOOCMe) 2 Pd(py) 2 [6].…”