Reaction of [Pt-4(mu-OCOCH3)(8)] (1) with 1 equiv of acrylic acid led to the selective monosubstitution of one of the four in-plane acetates in 1, affording [Pt-4([t-OCOCH3)(7)(mu-OCOCH=CH2)] (2a), whereas treatment with excess amounts of acrylic acid resulted in a full-substitution of four in-plane acetates, yielding [Pt-4(mu-OCOCH3)(4)(mu-OCOCH=CH2)(4)] (3). Similarly, monosubstituted heptaacetate complexes [Pt-4(4OCOCH3)(7) {mu-OCO(CH)(n)CH=CH2}] (2b-2d: n = 1-3) were prepared. Catalytic intermolecular coupling reactions of 2c and 2d assisted by Grubbs' catalysts gave the desired dimers [{Pt-4-(mu-OCOCH3)(7)}(2){mu-OCO(CH2)(n)CH=CH(CH2)(n)(mu-OCO)}] (6c: n = 2; 6d: n = 3).