Table 9. Overview on structurally characterized cations of group 14.

Cation	Anion	Class. a	Synthesis	Comment	Ref.
Homopolyatomic and cage cations
[C76]+	[HCB11H5Br6]–	Ox	C76 + [Ar3N]+[WCA]–		44
[C60]+	[HCB11H5Cl6]–	Ox	C60 + [Ar3N]+[WCA]–		259
[C60]2+	[AsF6]–	Ox	C60 + 3 AsF5	Polymeric	260
[HC60]+	[HCB11H5Cl6]–	Prot	C60 + H(WCA)		259
[C59N]+	[Ag(HCB11H5Cl6)2]–	Ox	(C59N)2 + 2[HBPC]˙+[WCA]–		261
	[B(C6F4H)4]–	Other			332
Onium ions
	[Al2Br7]–	Lewis			86
Enium ions
[(CH3)3C]+	[HCB11Me5Cl6]–	Hyd	n BuH + Me+[WCA]– or t BuH + Me(WCA)		265
[(CH3)3C]+	[Al2Br7]–	Lewis	t BuBr + 2 AlBr3		266
[(CH3)3C]+	[HCB11Cl11]–	Other	Thermal decomposition of [Et2Cl][CHB11Cl11]		267
	[HCB11Me5Br6]–	Hyd			265
	[HCB11Me5Br6]–	Hyd			265
	[HCB11I11]–	Lewis	p-CH3-C6F4-CF3 + Et3Si(WCA) + PhF		56
	[HCB11Cl11]–	Lewis	p-CH3-C6F4-CF3 + Et3Si(WCA) + PhF		56
	[As2F11]–	Lewis	C6H5CF3 + AsF5	Excess AsF5	268
	[HCB11I11]–	Lewis	p-F-C6H4CF3 + Et3Si(WCA) + PhF		56
	[HCB11I11]–	Lewis	CH3CF3 + Et3Si(WCA) + PhF		56
[CI3]+	[Al(ORPF)4]–	Salt	CI4 + Ag+[WCA]–		269
[CCl3]+	[Sb(OTeF5)6]–	Ox	CCl4 + [XeOTeF5]+[WCA]–		270
[CCl3]+	[Al(ORPF)4]–, [(RPFO)3Al-F-Al(ORPF)3]–	Salt	CCl4 + Ag+[WCA]–		271
[CBr3]+	[Sb(OTeF5)6]–	Ox	CBr4 + [XeOTeF5]+[WCA]–		270
[CBr3]+	[Al(ORPF)4]–, [(RPFO)3Al-F-Al(ORPF)3]–		CBr4 + Ag+[WCA]–		271
[C(OTeF5)3]+	[Sb(OTeF5)6]–	Ox	CBr4 + [XeOTeF5]+[WCA]–		270
	[Al(ORPF)4]–	Ox	CS2 + [AsBr4]+[WCA]– and CS2 + Br2 + Ag+[WCA]–		117
	[B(C6F5)4]–	Hyd			275
	[B(C6F5)4]–	Hyd			276
[Mes3Si]+	[HCB11Me5Br6]–	Other	Mes3Si(CH2CH CH2) + Et3Si(WCA)		24
[Pemp3Si]+	[B12Cl12]2–	Hyd	2Pemp2MeSiH + [Ph3C]2 +[WCA]–		290
[Pemp3Si]+	[Al(ORPF)4]–	Hyd	1.5Pemp2MeSiH + [Ph3C]+[WCA]–		291
	[B(C6F5)4]–	Ox			334
	[Al(ORPF)4]–	Salt	(Ar)3GeBr + Ag+[WCA]–	R = O t Bu	336
	[B(C6F5)4]–	Ox			335
[(Tipp)3Sn]+	[B(C6F5)4]–	Other	(allyl)(Tipp)3Sn + [E]+[WCA]–	[E]+ not exactly defined, likely [Et3Si(C6H6)]+ or comparable	34
	[B(C6F5)4]–	Com, Lig		R = Et, iPr	337
Delocalized (cyclic) cations
[C6H7]+	[HCB11Me5Br6]–	Prot	C6H6 + H(WCA)		386
	[HCB11H5Br6]–	Prot	C6H6 + H(WCA)		387
	[HCB11H5Br6]–	Prot	C6Me2H4 + H(WCA)		387
	[HCB11H5Br6]–	Prot	C6Me3H3 + H(WCA)		387
	[B(C6F5)4]–	Prot	Et3Si(WCA) + HCl + C6(Me)5H	C–H···F–C interactions	388
	[HCB11H5Br6]	Prot	C6Me6 + H(WCA)		387
[C6Me7]+	[AlCl4]–	Other	C6Me6 + CH3Cl + AlCl3		277
[C6F6]˙+	[Sb2F11]–	Ox	C6F6 + [O2]+[WCA]–	Crystallized out of HF	278
[C6F6]˙+	[Os2F11]–	Ox	C6F6 + OsF6 + SbF5	In HF	278
[C6Cl6]˙+	[Sb2F11]–	Ox	C6F6 + SbF5		279
[C6Br6]˙+	[As2F11]–	Ox	C6Br6 + [O2]+[AsF6]– + HSO3F		280
[C6I6]˙+	[AsF6]–	Ox	C6I6 + AsF5	In HF	279
[C6I6]˙+	[SbF6]–	Ox	C6I6 + SbF5	In HF	279
[C6I6]˙+	[OTf]–	Other	[C6I6][AsF6] + HOTf		279
[C6HF5]˙+	[AsF6]–	Ox	C6HF5 + [O2]+[WCA]–		279
	[SbF6]–	Ox	C6H2F4 + [O2]+[WCA]–		279
	[AsF6]–	Ox	C6H3F3 + [O2]+[WCA]– + AsF5		279
	[SbF6]–	Ox	C6H3F3 + [O2]+[Sb2F11]–	In HF	279
	[Sb2F11]–	Ox	C6F5(CF3) + [O2]+[WCA]–	In HF	280
	[Sb2F11]–	Ox	C6F4(CF3)2 + SbF5	In HF	280
	[Sb2F11]–	Ox	C6H2Cl4 + [O2]+[WCA]–		280
	[Sb3F16]–	Ox	[C6F5–C6F5] + [O2]+[WCA]– + SbF5		280
	[Nb2F11]–	Ox			281
	[SbF6]–	Ox			282
[Cy3C3]+	[SbF6]–	Salt	[Cy3C3]Cl + Ag+[WCA]–		283
[Cy2PhC3]+	[BF4]–	Lewis	[Cy2(Ph)C3]F + BF3		283
	[SbCl6]–	Prot			284
	[HCB11Me5Br6]–	Hyd	ArMe2SiH + [Ph3C]+[WCA]–		286
	[B(C6F5)4]–	Other			292
	[B(C6F4R)4]–	Other		R = 4-SiMe2 t Bu	293
	[Zr2Cl7Cp*2]–	Lewis			294
	[B(C6F5)4]–	Prot			295
	[B(C6H5)]–, [B(ArCF3 )4]–, [B(C6F4R)4]–	Other		R = 4-Si(Me)2( t Bu)	339–341
Ligand-stabilized cations
	[Sb2F11]–	Lewis			273
[I3C-PX3]+	[Al(ORPF)4]–	Comp	[CI3]+[WCA]– + PX3	X = Cl, Br, I	274
[I3C-PI3]+	[(RPFO)3Al-F-Al(ORPF)3]	Comp	[CI3]+[WCA]– + PI3		274
[I3C-AsI3]+	[Al(ORPF)4]–	Comp	[CI3]+[WCA]– + AsI3		274
	[HCB9H4Br5]–	Hyd	iPr3SiH + [Ph3C]+[WCA]– + MeCN		297
	[B(C6F5)4]–	Other	t Bu3Si–Si t Bu3 + 2[Ph3C]+[WCA]– + t BuCN		298
	[B(C6F5)4]–	Com		+ MeCN	299
[Fc3Sipy]+	[B(ArCF3 )4]–	Lig	[Fc3Si(THF)]+ + py		300
	[HCB11H5Br6]–	Ion	t Bu3Si(WCA) + H2O		301
	[HCB11Cl11]–	Ion	iPr3Si(WCA) + C6H4Cl2		81
	[HCB11Me5Br6]–	Ion	Et3Si(WCA) + SO2		81
	[OTf]–	Ion	Me2Si(OTf)2 + bipy		302
	[B(C6F5)4]–	Hyd	Me2ArSiH + [Ph3C]+[WCA]–		303
	[OTf]–	Ion	Me2Si(OTf)2 + 2DMAP		302
	[B(C6F5)4]–	Hyd	Et3SiH + [Ph3C]+[WCA]–		289
[Me3Si(Ar)]+	[B(C6F5)4]–	Lig	[Me3SiHSiMe3]+[WCA]– + arene	Ar = benzene, toluene, ethylbenzene, n-propylbenzene, and iso-propylbenzene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, mesitylene	304
	[B(C6F5)4]–	Hyd			76
[Me3SiHSiMe3]+	[HCB11HCl11]–	Hyd	2Me3SiH + [Ph3C]+[WCA]–		81
[Et3SiHSiEt3]+	[B(C6F5)4]–	Hyd	2Et3SiH + [Ph3C]+[WCA]–		306
[Me3SiXSiMe3]+	[B(C6F5)4]–	Ion	Me3SiX + Me3Si(WCA)	X = F, Cl, Br, I	307
[Me3Si-CN-SiMe3]+	[B(C6F5)4]–	Ion	Me3SiCN + Me3Si(WCA)		309
[Me3Si-OCN-SiMe3]+	[B(C6F5)4]–	Ion	Me3SiOCN + Me3Si(WCA)		309
[Me3Si-SCN-SiMe3]+	[B(C6F5)4]–	Ion	Me3SiSCN + Me3Si(WCA)		309
[(Me3Si)2NNN]+	[B(C6F5)4]–	Ion	Me3SiNNN + Me3Si(WCA)		309
	[B(C6F5)4]–	Ion	Me3Si(OTf) + Me3Si(WCA)		308
	[B(C6F5)4]–	Hyd			311
	[B(C6F5)4]–	Other			311
	[B(C6F5)4]–	Hyd		Ar = Tol	312
	[B(C6F5)4]–	Other	(Me3Si)3CSiMePhH + [Ph3C]+[WCA]–		313
	[B(C6F5)4]–	Other			314
	[B(C6F5)4]–	Other			314
	[B(C6F5)4]–	Other		X = Cl, Br	315
	[B12Cl12]2–	Hyd	2FcMe t BuSiH + [Ph3C]2 +[WCA]–		316
	[OTf]–	Lewis			317
	[OTf]–	Lewis			317
	[OTf]–	Lewis			317
	[OTf]–	Lewis			317
	[OTf]–	Lewis			317
	Cl–	Ion			318
	Cl–	Ox			318
	[OTf]–	Ox			319
	Cl–	Ion			320
	I–	Ion			321
	[OTf]–	Ox			319
		Other			319
	I–	Ion			321
	[B(C6F5)4]–	Ox	t Bu3Ge–Ge t Bu3 + 2[Ph3C]+[WCA]– + t BuCN		298
	[OTf]–	Ion	Me2Ge(OTf)2 + bipy		302
	[B(C6F5)4]–	Hyd			343
	[AlCl4]–	Ox			344
	[B(C6F5)4]–	Ox or Com			349
	[B(C6F5)4]–	Hyd			349
	I–	Ion			354
	[OTf]–	Ion, Lig			355
[Ge([12]-crown-4)2]2+	[GeCl3]–	Ion	GeCl2·dioxane + [12]crown-4		357
[Ge([12]-crown-4)2]2+	[OTf]–	Ion	GeCl2·dioxane + [12]crown-4 + 2Me3Si(OTf)		357
[GeCl([15]-crown-5)]+	[GeCl3]–	Ion	2GeCl2·dioxane + [15]crown-5		357
[Ge(OTf)([15]-crown-5)]+	[OTf]–	Ion	GeCl2·dioxane + [15]crown-5 + 2Me3Si(OTf)		357
[GeCl([18]-crown-6)]+	[GeCl3]–	Ion	2GeCl2·dioxane + 1.5[18]crown-6		357
	[GeCl3]–	Ion			360
	[GeCl3]–	Ion			361
	[AlCl4]–	Lewis			344
	[B12Cl12]2–	Com			344
	[HO{B(C6F5)3}2]–	Lewis			369
	[B(C6F5)4]–	Prot		Protonated by acidified benzene	365
	[B(C6F5)4]–	Prot			365
	[SbF6]–	Salt			80
	[SbF6]–	Lig			80
	[SbF6]–	Lig			80
	[Al(ORPF)4]–	Salt			366
	[Al(ORPF)4]–	Lig			366
	[B(C6F5)4]–	Lewis			347
[Me3Sn(OPPh3)2]+	[(MeSO2)2N]–	Ion	Me3SnN(SO2Me)2 + 2OPPh3		342
	[B(Ph)4]–	Ox		L = DMAP	345
[Sn([15]crown-5)2]2+	[SnCl3]–	Ion	2SnCl2 + 2[15]crown-5		350
[Sn([12]crown-4)2]2+	[OTf]–	Ion	Sn(OTf)2 + 2[12]crown-4		352
[Sn([15]crown-5)2]2+	[OTf]–	Ion	Sn(OTf)2 + 2[15]crown-5		352
[Sn([18]crown-6)(OTf)]+	[OTf]–	Ion	Sn(OTf)2 + [18]crown-6		352
[Sn([18]crown-6)(F)]+	[PF6]–	Other	[Sn([18]crown-6)]2+[WCA]2 – + KF		353
	[OTf]–	Ion	Sn(OTf)2 + cryptand[2.2.2] or 2SnCl2 + cryptand[2.2.2] + 4Me3Si(OTf)		356
	[SnCl3]–	Ion	2SnCl2 + cryptand[2.2.2]		356
	[SnBr3]–	Ion	2SnCl2 + cryptand[2.2.2] + 4Me3SiBr		356
	[B(C6F5)4]–	Com			346
	[B(C6F5)4]–	Other			348
	[SnCl3]–	Salt			389
	[GeBr3]–	Ion	GeBr2 + bipy	Bulk product is GeBr2(bipy)	359
	[GeCl3]–	Ion	GeCl2·dioxane + pmdta		359
	Cl–	Ion			363
	Cl–	Ox			363
	Cl–	Ion			364
	[GeCl3]–	Ion	GeCl2·dioxane + Me4-cyclam		358
	[GeBr3]– + Br–	Ion	GeBr2 + Me3-tacn		358
	[SnCl3]–	Ion			360
	[SnCl3]–	Ion			361
	[SnBr3]–	Ion		Ar = 2,5- t Bu2(C6H3)	362
	[SnCl3]–	Ion		Ar = 2,5- t Bu2(C6H3) and 2,6-Me2(C6H3)	362
	[Al(ORPF)4]–	Salt			366
	[Al(ORPF)4]–	Lig			366
	[MeB(C6F5)3]–	Lewis			367
	[SbF6]–	Salt			368
	[B(Ph)4]–	Salt			345
	[B(ArCF3 )4]–	Salt			345
	[B(C6F5)4]–	Other	(Tipp)2Sn + [Et3Si(C7H8)]+[WCA]–		371
[Pb(NO3)([12]-crown-4)2]+	[Pb(NO3)3([12]crown-4)]–	Ion	Pb(NO3)2 + [12]crown-4		351
[Pb([15]-crown-5)2]2+	[Pb(NO3)3([15]crown-5)]–	Ion	Pb(NO3)2 + 2[15]crown-5		351
[Pb(benzo-[15]-crown-5)2]2+	[Pb(NO3)3(benzo-[15]crown-5)]–	Ion	Pb(NO3)2 + benzo-[15]crown-5		351
	[B(C6F5)4]–	Salt			367
	[B(C6F5)3(CH3)]–	Lewis			370
Cyclopentadienyl substituted cations
	[B(C6F5)4]–	Prot	(Me5C5)2Si + [Me5C5H2]+[WCA]–		322
	[Al(ORPF)4]–	Prot	(Me5C5)(iPr5C5)Si + [H(OEt2)2]+[WCA]–		323
	[B(C6F5)4]–	Com	[(Me5C5)Si]+[WCA]– + dme		324
	[B(C6F5)4]–	Com	[(Me5C5)Si]+[WCA]– + [12]crown-4		324
	[BF4]–	Prot	(C5Me5)2Ge + H(WCA)		376
	[SnCl3]–	Lewis	(C5Me5)GeCl + SnCl2		377
	[BF4]–	Prot	(C5Me5)2Ge + H(WCA)		373
	[B(C6F5)4]–	Salt	(C5Me5)SnCl + Li+[WCA]–		375
	[B(C6F5)4]–	Salt	(C5Me5)PbCl + Li+[WCA]–		375
	[Ga(C6F5)4]–	Other	(C5Me5)2Sn + Ga(C6F5)3		378
	[B(C6F5)4]–	Com	[(C5Me5)Sn]+[WCA]– + (C5Me5)2Sn		375
	[B(C6F5)4]–	Com	[(C5Me5)Pb]+[WCA]– + (C5Me5)2Pb		375
Ion-like compounds
Me2(B12Cl12)		Salt	[Li]2 +[WCA]– + 2.2MeF + 2.6AsF5	1 : 1 mixture with [Li]2 +[WCA]–	288
(Me2CH)(HCB11Me5Br6)		Lewis	(H3C)2CHCl + (H3C)(HCB11H5Br6)		287
Me2CF(AsF6)		Lewis	(H3C)2CF2 + AsF5		268
(m-CF3-C6H4)(Ph)CF(AsF6)		Lewis	C6H5CF3 + AsF5		268
Me3Si(HCB11F11)		Hyd	Me3SiH + [Ph3C]+[WCA]–		326
Me3Si(C2H5CB11F11)		Hyd	Me3SiH + [Ph3C]+[WCA]–		326
Me3Si(FAl(ORPF)3)		Other	Ag+[Al(ORPF)4]– + Me3SiCl or AlEt3 + 3HORPF + Me3SiF		327
Et3Si(HCB11H5Br6)		Hyd	Et3SiH + [Ph3C]+[WCA]–		328
Et3Si(HCB11Cl11)		Hyd	Et3SiH + [Ph3C]+[WCA]–		81
iPr3Si(HCB11H5Br6)		Hyd	iPr3SiH + [Ph3C]+[WCA]–		325
iPr3Si(HCB11H5Cl6)		Hyd	iPr3SiH + [Ph3C]+[WCA]–		329
iPr3Si(HCB11H5I6)		Hyd	iPr3SiH + [Ph3C]+[WCA]–		329
iPr3Si(HCB9H4Br5)		Hyd	iPr3SiH + [Ph3C]+[WCA]–		297
t Bu3Si(HCB11H5Br6)		Hyd	t Bu3SiH + [Ph3C]+[WCA]–		328
t Bu3Si(FAl(ORPF)3)		Other	t Bu3SiI + 15 ( t Bu)3SiF + Ag+[Al(ORPF)4]–		330
t Bu2MeSi(HCB11H5Br6)		Hyd	t Bu2MeSiH + [Ph3C]+[WCA]–		328
Fc3Si(OTf)		Prot			331
Et3Ge(HCB11H5Br6)		Hyd	Et3GeH + [Ph3C]+[WCA]–		338
Et3Sn(HCB11H5Br6)		Lewis	Et3SnCl + (Et)3Si(WCA)		338
n Bu3Sn(CB11Me12)		Ox	n Bu6Sn2 + 2 CB11Me12		333
Et3Pb(HCB11H5Br6)		Lewis	Et3PbCl + (Et)3Si(WCA)		338
Transition-metal substituted cations
	[B(C6F5)4]–	Salt			380
	[PF6]–	Salt			379
	[BF4]–	Com			381
		Salt			382
	[CB11H12]–	Salt		L = THF	382
	[ClO4]–	Ion			383
	[ClO4]–	Ion			383
	[W(CO)3Cp]–	Prot			384
	[AlBr4]–	Lewis			385
	[B(ArCl)4]–	Salt			385
{(Cy3P)2Pt}2Sn(AlBr4)2		Lewis			385
	[AlCl4]–	Lewis			385
	[B(ArCl)4]–	Salt			385
	[AlCl4]–	Salt			385
{(Cy3P)2Pt}2Pb(AlCl4)2		Lewis			385