81:, some vanadium(III) is reduced to inactive vanadium(II) derivatives. To correct for this reduction, reoxidants such as methyl trichloroacetate are added. The alkyl chloride functions as a source of a chlorine radical, which adds to the inactive V(II) species. In some cases, the reoxidants are called
139:
Timothy J. Donohoe; Katherine M. P. Wheelhouse (née Gosby); Peter J. Lindsay-Scott; Paul A. Glossop; Ian A. Nash; Jeremy S. Parker (2008). "Pyridine-N-Oxide as a Mild
Reoxidant Which Transforms Osmium-Catalyzed Oxidative Cyclization".
210:
R. A. Miller; R. S. Hoerrner (2003). "Iodine as a
Chemoselective Reoxidant of TEMPO: Application to the Oxidation of Alcohols to Aldehydes and Ketones".
57:. The spent catalyst is an osmium(VI) complex, which reacts with a reoxidant to regenerate Os(VIII). Typical reoxidants for this application include
138:
73:
As catalysts for the polymerization of dienes, vanadium complexes are activated with alkylaluminium chlorides, e.g.
32:
by oxidation. In some cases they are used stoichiometrically, in other cases only small amounts are required.
175:
Kotohiro Nomura; Shu Zhang (2011). "Design of
Vanadium Complex Catalysts for Precise Olefin Polymerization".
250:
77:. The organoaluminium reagent installs alkyl groups on the V(III) precatalyst. During catalysis or during
62:
260:
74:
8:
101:
as the reoxidant, TEMPO-H is oxidized back to TEMPO, which then functions catalytically:
78:
255:
227:
192:
157:
97:, is an expensive but effective oxidant for converting alcohols to carbonyls. With
219:
184:
149:
58:
50:
244:
231:
196:
161:
153:
223:
188:
17:
29:
25:
98:
54:
94:
68:
93:(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl, commonly known as
209:
174:
49:
Reoxidants are commonly used in reactions catalyzed by
53:, which is a primary oxidant converting alkenes to
40:
242:
69:Vanadium(III)-based alkene polymerizations
88:
243:
112:OH + 2 TEMPO → RCHO + 2 TEMPO-H
13:
14:
272:
35:
203:
168:
132:
1:
126:
7:
45:-catalyzed dihydroxylations
10:
277:
63:N-methylmorpholine N-oxide
61:, ferricyanide/water, and
75:diethylaluminium chloride
154:10.1002/anie.200705425
89:Oxidations with TEMPO
142:Angew. Chem. Int. Ed
251:Reaction mechanisms
122:→ 2 TEMPO + 2 HI
79:catalyst activation
28:that regenerates a
224:10.1021/ol0272444
189:10.1021/cr100207h
148:(15): 2872–2875.
268:
261:Oxidizing agents
236:
235:
207:
201:
200:
183:(3): 2342–2362.
172:
166:
165:
136:
59:pyridine-N-oxide
51:osmium tetroxide
276:
275:
271:
270:
269:
267:
266:
265:
241:
240:
239:
208:
204:
173:
169:
137:
133:
129:
121:
118:2 TEMPO-H + I
111:
91:
71:
47:
44:
38:
12:
11:
5:
274:
264:
263:
258:
253:
238:
237:
218:(3): 285–287.
202:
167:
130:
128:
125:
124:
123:
119:
113:
109:
90:
87:
70:
67:
46:
42:
39:
37:
34:
9:
6:
4:
3:
2:
273:
262:
259:
257:
254:
252:
249:
248:
246:
233:
229:
225:
221:
217:
213:
206:
198:
194:
190:
186:
182:
178:
171:
163:
159:
155:
151:
147:
143:
135:
131:
117:
114:
107:
104:
103:
102:
100:
96:
86:
84:
80:
76:
66:
64:
60:
56:
52:
33:
31:
27:
23:
19:
215:
211:
205:
180:
176:
170:
145:
141:
134:
116:reoxidation:
115:
105:
92:
83:rejuvenators
82:
72:
48:
36:Applications
21:
15:
245:Categories
127:References
106:oxidation:
256:Catalysis
212:Org. Lett
177:Chem. Rev
22:reoxidant
18:chemistry
232:12556173
197:21033737
162:18324650
30:catalyst
55:glycols
26:reagent
230:
195:
160:
99:iodine
95:TEMPO
24:is a
228:PMID
193:PMID
158:PMID
20:, a
220:doi
185:doi
181:111
150:doi
108:RCH
41:OsO
16:In
247::
226:.
214:.
191:.
179:.
156:.
146:47
144:.
85:.
65:.
234:.
222::
216:5
199:.
187::
164:.
152::
120:2
110:2
43:4
Text is available under the Creative Commons Attribution-ShareAlike License. Additional terms may apply.