Table 1.

Experimental AEs in DI of (CH₃)AuP(CH₃)₃ compared to the threshold values calculated at the TPSS/def2-TZVP and DLPNO-CCSD(T)/QZVPP levels of theory. The best agreements between experiment and theory and the respective reaction paths are signified in bold.

m/z	Product	TPSS-TZVP	DLPNO-CCSD-QZVPP	AE (eV)
288	[(CH3)AuP(CH3)3]+	7.45	7.58	7.5 ± 0.2
273	[AuP(CH3)3]+ + (CH3)	8.59	8.38	8.1 ± 0.2
	[(CH3)AuP(CH3)2]+ + (CH3)	10.20	10.44
76	[P(CH3)3]+ + (CH3)Au	9.38	9.17	8.6 ± 0.2
	[HP(CH3)2(CH2)]+ + (CH3)Au	9.73	9.61
	[P(CH3)3]+ + (CH3) + Au	12.04	11.54
75	[P(CH3)2(CH2)]+ + (CH3)AuH	10.64	10.68	10.5 ± 0.2
	[P(CH3)2(CH2)]+ + (CH3)Au + H	12.12	11.86
	[HP(CH3)(CH2)2]+ + (CH3)AuH	12.62	12.90
61	[HP(CH3)(CH2)]+ + (CH3)2Au	11.16	11.20	11.1 ± 0.2
	[HP(CH3)(CH2)]+ + C2H6 + Au	11.22	10.43
	[P(CH3)2]+ + (CH3)2Au	11.64	11.62
59	[P(CH2)2]+ + (CH3)2Au + H2	13.46	13.45	13.4 ± 0.3
	[P(CH2)2]+ + (CH3)AuH + CH4	13.18	12.93
	[P(CH2)2]+ + H2Au + C2H6	13.56	13.07
	[HP(CH2)CH]+ + (CH3)2Au + H2	15.22	15.61
45	[PCH2]+ + (CH3)AuH + 2(CH3)	17.50	17.04	13.6 ± 0.4
	[PCH2]+ + (CH3)AuH + C2H6	13.84	13.20
	[PCH2]+ + Au(CH3) + C2H6 + H	15.32	14.38
	[PCH2]+ + (CH3)Au(CH3) + CH4	13.50	13.06
	[PCH2]+ + Au + (CH3) + C2H6 + H	17.98	16.76
	[HPCH]+ + (CH3)AuH + C2H6	16.19	15.97
	[PCH2]+ + AuH + (CH3) + C2H6	14.85	13.75
	[HPCH]+ + AuH + (CH3) + C2H6	17.19	16.52