and break-off distance data, we demonstrate that a PPh 3 supporting ligand in the platinum complexes can provide an alternative contact point for the STM tip in the molecular junctions, orthogonal to the terminal CuCSiMe 3 group. The attachment of hexyloxy side chains to the diethynylbenzene ligands, e.g. trans-Pt{CuCC 6 H 2 (Ohex) 2 CuCSiMe 3 } 2 (PPh 3 ) 2 (Ohex = OC 6 H 13 ), hinders contact of the STM tip to the PPh 3 groups and effectively insulates the molecule, allowing the conductance through the full length of the backbone to be reliably measured. The use of trialkylphosphine (PEt 3 ), rather than triarylphosphine (PPh 3 ), ancillary ligands at platinum also eliminates these orthogonal contacts. These results have significant implications for the future design of organometallic complexes for studies in molecular junctions.