Four porous heterometallic coordination polymers were synthesized via a metalloligand strategy. All of them contain the [Pd(diimine)Cl(2)] moiety, which has good catalytic activity, and present remarkable versatility for catalysing Suzuki-Miyaura and Heck reactions.

Bidentate monoanionic ligands 2-(benzo[d]thiazol-2-yl) phenol (La), 2-(benzo[d]thiazol-2-yl)-6-methylphenol (Lb), 2-(benzo[d]thiazol-2-yl)-6-tert-butyl-4-methylphenol (Lc), 2-(benzo[d]thiazol-2-yl)-6-chlorophenol (Ld), and 2-(benzo[d]thiazol-2-yl)-4-chlorophenol (Le) have been synthesized. Reactions of TiCl4(THF)2 or ZrCl4 with La-Le afford the corresponding titanium complexes Ti[ON]2(R)Cl2 [R = 6-Me (2b); R = 4-Me-6-Bu(t) (2c)], and zirconium complexes Zr[ON]2(R)Cl2 [R = H (3a); R = 6-Me (3b); R = 4-Me-6-Bu(t) (3c); R = 6-Cl (3d); R = 4-Cl (3e)], and Zr[ON(R)]HCl4 x THF [R = 6-Me (4b)], respectively. Complexes 2a-4b were characterized by IR, 1H NMR spectra and elemental analysis. The molecular structures of La, 2b, 2c, 3b, 3c and 4b have been characterized by single-crystal X-ray diffraction analyses. The effect of steric hindrance and the coordination metal on the structure of the products has been investigated. When activated by excess methylaluminoxane (MAO), 2b and 2c, 3a-3e and 4b can be used as catalysts for ethylene polymerization and exhibit moderate to good activities.

Tridentate dianionic arylsulfide ligands [2-(2-SC 6 H 4 )NdCHC 6 H 4 O] 2-(La), [6-Me-2-(2-SC 6 H 4 )Nd CHC 6 H 3 O] 2-(Lb), and [4-Me-6-Bu t -2-(2-SC 6 H 4 )NdCHC 6 H 2 O] 2-(Lc) have been synthesized. Reactions of Ti(OPr i ) 4 and TiCl 4 with the tridentate dianionic arylsulfide ligands (La-Lc) afford monomeric and dimeric titanium complexes {Tirespectively. Hydrolysis of 4c in THF solution containing a small amount of water produces the tetranuclear complex {TiComplexes 2a-5c are characterized by 1 H NMR spectra and elemental analysis. The molecular structures of 2a, 2b, 2c, 3b, and 5c have been characterized by single-crystal X-ray diffraction analyses. The effect of steric hindrance on the structure of products has been investigated. When activated by excess methylaluminoxane (MAO), 2a-2c, 4a-4c, and 5c can be used as catalysts for ethylene polymerization and exhibit moderate to good activities.

Metallacyclic complexes [( Mes C-C meth )Pd(L)] 2 (OTf ) 4 ( Mes C-C meth = 1,1 0 -dimesityl-3,3 0 -methylenediimidazolin-2,2 0 -diylidene; L = 4,4 0 -dithiodipyridine (L 1 ) (5), 1,2-bis(4-pyridylthio)ethane (L 2 ) (6), 1,3-bis(4-pyridylthio)propane (L 3 ) ( 7)) were obtained by the self-assembly of [( Mes C-C meth )-Pd(CH 3 CN) 2 ](OTf ) 2 with flexible pyridine-based ligands L 1 -L 3 in high yields. The reaction of [( Mes C-C meth )Pd(CH 3 CN) 2 ](OTf ) 2 with a rigid pyrazine ligand led to the formation of mononuclear [( Mes C-C meth )Pd(pyrazine) 2 ](OTf ) 2 ( 4), which can be ascribed to the effect of the steric bulk of the substituent. Complexes 4-6 have been well characterized by elemental analyses, 1 H NMR and IR spectra, and single-crystal molecular structure analysis. † Part of the Dietmar Seyferth Festschrift. Dedicated to Professor Dr. Dietmar Seyferth on the occasion of his 80th birthday.

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