Metallomacrocycles containing {M(NO)(TpMe2)} [TpMe2 = HB(3,5-Me2C3HN2)3; M = Mo or W] have been synthesized by direct reaction between [M(NO)(TpMe2)I2] and a heterotopic ligand HE–E′H {1,x-HOC6H4XOH (x = 3, X = CO; x = 3 or 4, X = CH2 or CH2CH2)} in the presence of NEt3. Only DL and meso isomers were isolated from the reactions where M = Mo, x = 4 and X = CO or CH2CH2 but both DL and meso and syn and anti isomers from the other reaction mixtures. Stereo-controlled synthetic routes to syn and anti isomers containing the OC6H4CH2O-3 bridging ligand were developed through formation of [M(NO)(TpMe2)(OC6H4CHO-3)]2 (M = Mo or W) followed by reduction to [M(NO)(TpMe2)(OC6H4CH2OH-3)]2 and subsequent reaction with [M′(NO)(TpMe2)I2] (M′ = W or Mo) to give [{M(NO)(TpMe2)}(μ-OC6H4CH2O-3)2{M′(NO)(TpMe2)}]. The trinuclear complex [{Mo(TpMe2)(NO)}(μ-OC6H4CH2O-3)2{W(TpMe2)(NO)}2(μ-1,3-OC6H4O)] was obtained from the reaction of [Mo(NO)(TpMe2)(OC6H4CH2OH-3)]2 with the binuclear complex [{W(NO)(TpMe2)I}2(μ-1,3-O2C6H4)]. The crystal structures of DL -[Mo(TpMe2)(NO)(OC6H4CH2CH2O-4)]2 and [W(TpMe2)(NO)(OC6H3NO2-4-CH2CH2O-3)]2 were established.