147:
131:
297:
119:
159:
81:, the Mo-N distance is 163.7 pm. The occurrence of terminal nitrido ligands follow the patterns seen for oxo complexes: they are more common for early and heavier metals. Many bi- and polynuclear complexes are known with bridging nitrido ligands. More exotic metal nitrido complexes are also possible, such as a recently reported compound containing a terminal uranium nitride (-U≡N) bond.
107:
91:
554:
Laplaza, Catalina E.; Johnson, Marc J. A.; Peters, Jonas C.; Odom, Aaron L.; Kim, Esther; Cummins, Christopher C.; George, Graham N.; Pickering, Ingrid J. (1996). "Dinitrogen
Cleavage by Three-Coordinate Molybdenum(III) Complexes: Mechanistic and Structural Data1".
260:
The nitride ligand can be both electrophilic and nucleophilic. Terminal nitrides of early metals tend to be basic and oxidizable, whereas nitrides of the later metals tend to be oxidizing and electrophilic. The former behavior is illustrated by their
504:
Reiners, Matthias; Maekawa, Miyuki; Daniliuc, Constantin G.; Freytag, Matthias; Jones, Peter G.; White, Peter S.; Hohenberger, Johannes; Sutter, Jörg; Meyer, Karsten; Maron, Laurent; Walter, Marc D. (2017).
293:. In some cases, the nitride is completely encased in the center of six or more metals and cannot undergo reactions, although it contributes to the intermetallic bonding.
582:
Dehnicke, Kurt; Weller, Frank; Strähle, Joachim (2001). "Nitrido bridges between transition metals and main group elements illustrated by the series NNa to NCl".
1191:
1228:
1404:
1078:
732:
1422:
1258:
1427:
1295:
62:
proceeds via nitrido intermediates. Nitrido complexes have long been known, the first example being salts of , described in the 19th century.
428:
King, David M.; Tuna, Floriana; McInnes, Eric J. L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. (2012).
1314:
1385:
1109:
118:
507:"Reactivity studies on [Cp′Fe(μ-I)]2: Nitrido-, sulfido- and diselenide iron complexes derived from pseudohalide activation"
1045:
478:
1250:
1058:
929:
354:
42:. The distinction between the molecular and solid-state polymers is not always very clear as illustrated by the materials Li
1364:
1215:
1136:
1083:
725:
1101:
1053:
319:
130:
1376:
1331:
1287:
1271:
1073:
1040:
1030:
917:
1417:
1326:
1183:
982:
679:
626:
1279:
1242:
1237:
1203:
994:
959:
942:
934:
870:
810:
1453:
1088:
861:
849:
820:
815:
718:
289:, several metal clusters are known to contain nitride ligands at their center. Such nitrido ligands are termed
1164:
1068:
1022:
905:
825:
779:
233:
164:
90:
837:
314:
106:
1448:
1356:
1178:
892:
200:
Metal nitrides are produced using a variety of nitrogen sources. The first example above is prepared from
146:
70:
Mononuclear complexes feature terminal nitride ligands, typically with short M-N distances consistent with
485:. Vol. 2. Translated by Stecher, Paul G. (2nd ed.). NY, NY: Academic Press. p. 1605.
71:
701:
648:
1340:
900:
755:
1128:
58:. Transition metal nitrido complexes have attracted interest in part because it is assumed that
16:
Coordination compounds and metal clusters containing a nitrogen atom bound to a transition metal
1223:
1035:
75:
346:
290:
23:
1014:
741:
441:
241:
158:
8:
445:
1409:
1155:
760:
689:
636:
531:
506:
137:
30:
that contain an atom of nitrogen bound only to transition metals. These compounds are
671:
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622:
536:
486:
459:
350:
59:
39:
667:
614:
591:
564:
526:
518:
449:
410:
401:
Dehnicke, Kurt; Strähle, Joachim (1992). "Nitrido
Complexes of Transition Metals".
383:
338:
97:
286:
1173:
887:
618:
244:
is an effective reagent to give chloro-nitrido complexes. In some cases, even N
1442:
882:
787:
387:
27:
454:
429:
540:
463:
414:
296:
232:
Most commonly however, nitrido complexes are produced by decomposition of
947:
710:
262:
201:
609:
Smith, Jeremy M. (2014). "Reactive
Transition Metal Nitride Complexes".
522:
266:
568:
664:
Organometallic Metal
Clusters Containing Nitrosyl and Nitrido Ligands
595:
270:
371:
236:. The driving force for these reactions is the great stability of N
249:
35:
490:
430:"Synthesis and Structure of a Terminal Uranium Nitride Complex"
503:
124:, containing two W(VI) centres bridged by a nitrido ligand.
553:
427:
285:
Owing to the ability of nitrido ligands to serve as a
581:
34:, i.e. discrete in contrast to the polymeric, dense
273:
to give iminophosphine derivatives containing the R
403:Angewandte Chemie International Edition in English
337:
1440:
400:
369:
269:. Ru and Os nitrido complexes often add organo
255:
726:
483:Handbook of Preparative Inorganic Chemistry
740:
733:
719:
661:
479:"The platinum metals: Potassium osmiamate"
611:Progress in Inorganic Chemistry Volume 58
530:
453:
252:can serve as sources of nitride ligands.
50:and more condensed derivatives such as Na
557:Journal of the American Chemical Society
295:
280:
1441:
714:
608:
476:
325:
195:
112:, a square pyramidal Mo(VI) complex.
65:
320:Transition metal dinitrogen complex
300:This series is known for M = Fe(CO)
13:
613:. Vol. 58. pp. 417–470.
370:Fritzsche, J.; Struve, H. (1847).
14:
1465:
493:– via the Internet Archive.
666:. Vol. 24. pp. 41–86.
157:
145:
129:
117:
105:
89:
74:. For example, in the anion in
655:
85:Example metal nitrido complexes
602:
575:
547:
497:
470:
421:
394:
363:
331:
1:
672:10.1016/S0065-3055(08)60413-X
662:Gladfelter, Wayne L. (1985).
376:Journal für Praktische Chemie
372:"Ueber die Osman-Osmiumsäure"
315:Abiological nitrogen fixation
38:materials that are useful in
256:Reactions of nitrido ligands
7:
308:
72:metal ligand multiple bonds
10:
1470:
619:10.1002/9781118792797.ch06
481:. In Brauer, Georg (ed.).
477:Grube, H. L. (1956).
152:A uranium nitrido complex.
136:, structurally related to
1397:
1307:
1148:
1121:
1007:
975:
803:
772:
748:
343:Chemistry of the Elements
341:; Earnshaw, Alan (1997).
388:10.1002/prac.18470410113
455:10.1126/science.1223488
20:Metal nitrido complexes
1454:Coordination complexes
742:Coordination complexes
415:10.1002/anie.199209551
305:
24:coordination compounds
347:Butterworth-Heinemann
339:Greenwood, Norman N.
299:
281:Interstitial nitrides
96:, isoelectronic with
242:Nitrogen trichloride
1449:Inorganic chemistry
446:2012Sci...337..717K
208:) as the N source:
523:10.1039/C7SC00570A
326:General references
306:
196:Preparative routes
138:basic iron acetate
1436:
1435:
569:10.1021/ja960574x
563:(36): 8623–8638.
440:(6095): 717–720.
356:978-0-08-037941-8
66:Structural trends
60:nitrogen fixation
40:materials science
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517:(5): 4108–4122.
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345:(2nd ed.).
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98:osmium tetroxide
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287:bridging ligand
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234:azido complexes
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698:|journal=
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645:|journal=
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601:
590:(2): 125–135.
584:Chem. Soc. Rev
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382:(1): 97–113.
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375:
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342:
333:
291:interstitial
284:
259:
231:
199:
69:
31:
19:
18:
277:PN ligand.
263:protonation
1443:Categories
1059:amino acid
976:Si donors:
271:phosphines
267:alkylation
1308:S donors:
1149:O donors:
1122:P donors:
1084:porphyrin
1031:imidazole
1008:N donors:
804:C donors:
773:B donors:
749:H donors:
700:ignored (
690:cite book
647:ignored (
637:cite book
32:molecular
541:30155215
491:63-14307
464:22745250
309:See also
250:nitriles
922:& C
532:6099922
442:Bibcode
434:Science
224:N + H
220:→ KOsO
165:((t-Bu)
36:nitride
830:＝CH-CH
678:
625:
539:
529:
489:
462:
353:
265:and N-
216:+ KNH
821:HC(O)
816:RC(O)
202:amide
1224:acac
1196:/HCO
1079:bipy
838:C(CH
702:help
676:ISBN
649:help
623:ISBN
537:PMID
487:LCCN
460:PMID
351:ISBN
248:and
26:and
22:are
1319:NCS
1296:OPR
1272:OSR
1251:ClO
1238:ONO
1216:RCO
1093:Si)
1089:(Me
1074:RCN
1041:RNO
989:4−n
987:SiR
943:≡CR
935:=CR
930:RNC
854:＝CH
668:doi
615:doi
592:doi
565:doi
561:118
527:PMC
519:doi
450:doi
438:337
411:doi
384:doi
212:OsO
204:(NH
76:PPh
54:MoN
46:MoN
1445::
1423:Br
1418:Cl
1386:NC
1377:SR
1357:SO
1327:RS
1288:PO
1280:SO
1267:NO
1243:NO
1233:CO
1192:CO
1174:RO
1137:PR
1129:PR
1113:CS
1069:RN
1054:py
1046:NO
1036:NO
1015:NH
999:Si
924:70
920:60
893:CO
888:CO
883:CN
862:RC
850:CH
826:CH
780:BR
694::
692:}}
688:{{
674:.
641::
639:}}
635:{{
621:.
588:30
586:.
559:.
535:.
525:.
513:.
509:.
458:.
448:.
436:.
432:.
407:31
405:.
380:41
378:.
374:.
349:.
261:N-
240:.
181:Fe
1428:I
1412:2
1410:F
1405:F
1388:S
1381:O
1379:2
1371:3
1369:O
1367:2
1365:S
1359:2
1351:2
1349:S
1347:2
1345:C
1343:2
1341:R
1336:S
1334:2
1332:R
1321:2
1317:2
1315:R
1298:3
1290:4
1282:4
1274:2
1265:5
1263:H
1261:5
1259:C
1253:4
1245:3
1231:2
1229:R
1218:2
1210:4
1208:O
1206:2
1204:C
1198:3
1194:3
1186:2
1184:O
1179:O
1169:O
1167:2
1165:R
1160:O
1158:2
1156:H
1139:2
1131:3
1111:N
1104:2
1102:N
1097:N
1095:2
1091:3
1064:N
1048:2
1025:3
1023:N
1017:3
997:3
995:R
985:n
983:H
966:7
964:H
962:9
960:C
954:5
952:H
950:5
948:C
937:2
918:C
912:6
910:R
908:6
906:C
901:C
895:2
877:4
875:H
873:6
871:C
866:R
864:2
856:2
852:2
844:3
842:)
840:2
832:2
828:2
811:R
794:n
792:H
790:m
788:B
782:2
763:2
761:H
756:H
734:e
727:t
720:v
704:)
684:.
670::
651:)
631:.
617::
598:.
594::
571:.
567::
543:.
521::
515:8
466:.
452::
444::
417:.
413::
390:.
386::
359:.
304:.
302:3
275:3
246:2
238:2
228:O
226:2
222:3
218:2
214:4
206:2
190:.
187:2
185:N
183:2
179:2
177:)
175:2
173:H
171:5
169:C
167:3
140:.
100:.
78:4
56:3
52:3
48:4
44:6
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