ExperimentalGeneral Remarks. All manipulations were performed in air, except where otherwise noted. The solvents thf and hexane (analytical grade) were freshly distilled from sodium/potassium alloy, dichloromethane was distilled from calcium hydride, the other solvents (acetonitrile, diethylether, acetone) were used as purchased. Deuterated solvents for NMR measurements were distilled from the appropriate drying agents under N 2 immediately prior to use following standard literature methods. 15 Air-sensitive compounds were stored and weighed in a glovebox. The reagents 1,2-dibromoethane, 1,3dibromopropane, 1,4-diiodobutane, 2,6-dimethylaniline, 2,4,6-trimethylaniline, 2,6-diisopropylaniline, triethylorthoformate, sodium tetrafluoroborate, and potassium bis(trimethylsilyl)amide were used as received. 1 H and 13 C NMR spectra were obtained on Bruker Avance AMX 400, 500 or Jeol Eclipse 300 spectrometers. The chemical shifts are given as dimensionless values and are frequency referenced relative to TMS. Coupling constants J are given in hertz (Hz) as positive values regardless of their real individual signs. Abbreviations used: st = septet, br = broad. Mass spectra (MS) and high-resolution mass spectra (HRMS) were obtained in positive electrospray (ES) mode unless otherwise reported, on a Waters Q-TOF micromass spectrometer. 1,3-Bis-(2,4,6-trimethylphenyl)-4,5,6,7-tetrahydro-3H-[1,3]diazepin-1-ium iodide, 7-Mes•HI. The reaction was performed on a 71.0 mmol scale of amidine (19.90 g), 5.00 g of K 2 CO 3 (36.0 mmol) and 22.00 g of 1,4-diiodobutane (71.0 mmol) in 1 L of acetonitrile. The solution was heated under reflux for 5 hours to yield 29.20 g (63.0 mmol, 89%) of white, crystalline material. 1,3-Bis-(2,6-dimethylphenyl)-4,5,6,7-tetrahydro-3H-[1,3]diazepin-1-ium iodide, 7-Xyl•HI. The reaction was performed on a 43.3 mmol scale of amidine (10.93 g), 5.8 mL of 1,4-diiodobutane (13.63 g, 44 mmol), 3.01 g of K 2 CO 3 (22.5 mmol) in 0.5 L of acetonitrile. The solution was heated under reflux for 5 hours to yield 14.85 g (34.2 mmol, 79%) of white, crystalline material. 1,3-Bis-(2,6-diisopropylphenyl)-4,5,6,7-tetrahydro-3H-[1,3]diazepin-1-ium iodide, 7-Pr i •HI. The reaction was performed on a 11.0 mmol scale of amidine (4.00 g), 0.78 g of K 2 CO 3 (5.6 mmol), 1.6 mL of 1,4-diiodobutane (3.76 g, 12.1 mmol) in 400 mL of acetonitrile. The solution was heated under reflux for 17 hours to yield 3.87 g (7.1 mmol, 64%) of white, crystalline material. 2,4-Bis-(2,4,6-trimethylphenyl)-4,5-dihydro-1H-benzo[e][1,3]diazepin-2-ium bromide, Xyl7-Mes•HBr. The reaction was performed on a 35.8 mmol scale of amidine (10.03 g), 36.0 mmol of , 'dibromo-o-xylene (9.49 g), 2.49 g of K 2 CO 3 (18.0 mmol) in 0.5 L of acetonitrile. The solution was heated under reflux for 5 hours to yield 12.42 g (26.2 mmol, 73%) of white, crystalline material. 1 H

Wrong way round: Imidazolium salts blocked at C2 undergo oxidative addition to a Pt0 center at C4/C5 (see scheme; nbe=norbornene, IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene). The resulting carbene ligands, which are bound the “wrong way” are susceptible, in common with their “normal” counterparts, to reductive elimination reactions to regenerate Pt0 complexes and imidazolium salts.

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