Reactions of internal alkynes with R3M-H (M = Si, Ge, Sn) follow an Unconventional trans-addition mode in the presence of [Cp*Ru(MeCN)(3)]PF6 (1) as the catalyst; however, the regioselectivity is often poor with the unsymmetrical substrates. This problem can be solved upon switching to a catalyst comprising a [Ru-Cl] bond, provided that acetylene derivative carries a protic functional group. The R3M unit is then delivered With high selectivity to the alkyne-C atom proximal to this steering substituent. This directing effect originates from the ability of the polarized [Ru-Cl] bond to engage in hydrogen bonding with the protic substituent, which helps upload, activate, and lock the alkyne within the coordination sphere. An additional interligand contact of the chloride with the -MR3 center positions the incoming reagent in a matching orientation that :translates into high regioselectivity. The proposed secondary interactions within the loaded catalyst are in line With a host of preparative and spectral data and With the Structures of novel ruthenium pi-complexes 10 and 11 in the solid state. Moreover, the first X-ray structure of a [Ru(pi-stannane)] Complex (12a) is presented, which indeed features peripheral Ru-Cl center dot center dot center dot MR3. contacts, this adduct also corroborates that alkyne-trans-addition chemistry likely involves. sigma-complexes as reactive intermediates. Finally, it is discussed that interligand cooperativity might constitute a more general principle that extends to mechanistically distinct transformations. The presented data therefore make an interesting case for organometallic chemistry that provides inherently better results when applied to substrates containing Unprotected rather than protected -OH, -NHR, or -COOH groups.