Cross-coupling　reactions　involving　metal　carbene　intermediates　play　an　increasingly　important　role　in　C–C　bond　formation.　Expanding　the　carbene　precursors　to　a　broader　range　of　starting　materials　and　more　diverse　products　is　an　ongoing　challenge　in　synthetic　organic　chemistry.　Herein,　we　report　a　Suzuki-Miyaura　coupling　reaction　of　in　situ-generated　Pd–carbene　complexes　via　desulfurization　of　thioureas　or　thioamides.　This　strategy　enables　the　preparation　of　a　broad　array　of　substituted　amidinium　salts　and　unsymmetrical　diaryl　ketones.　The　reaction　is　readily　scalable,　compatible　with　bromo　groups　on　aromatic　rings,　tolerant　to　moisture　and　air and　has　a　broad　substrate　scope.　Furthermore,　a　single　crystal　structure　of　Pd-diaminocarbene　complex　is　obtained　and　proven　to　be　the　key　intermediate　in　both　catalytic　and　stoichiometric　reactions.　Preliminary　mechanistic　studies　demonstrate　the　dual　role　of　the　silver　salt　as　a　desulfurating　reagent　assisting　the　elimination　of　sulfur　and　as　oxidant　facilitating　the　PdII/Pd0/PdII　catalytic　cycle.　©　2019,　The　Author(s).