73:
420:
165:. The reaction mechanisms are more complicated than this simple scenario. Condensation of low-molecular-weight metal carbonyls requires decarbonylation, which can be induced thermally, photochemically, or using various reagents. The nuclearity (number of metal centers) of binary metal carbonyl clusters is usually no greater than six.
127:(1928–1980) was a pioneer for the synthesis and characterization of high-nuclearity metal carbonyl clusters. His first studies started in 1958, in the attempt to repeat a patent that claimed an improved selectivity in hydroformylation. From a mixture of iron and cobalt carbonyls the first bimetallic carbonyl cluster HFeCo
390:
Chini clusters can also be converted heterometal clusters and catalyze pH driven redox reactions and transport. First, the Chini clusters are the source of platinum atoms for the mixed metal cluster synthesis. For instance, the reaction with produces heterometal cluster . Second, the Chini clusters
382:
clusters. Within a triangular unit, the platinum–platinum bond lengths are 2.65 Å and between units the Pt–Pt bond lengths are 3.05 Å. Cluster structure is easily disrupted by deposition onto surfaces such as carbon or silicon, where the chains are broken, but the triangular subunits remain intact.
377:
Chini clusters are based on a planar triangular building block that can be condensed as multiple units forming chains usually anywhere from two to ten units long. The chains are formed by stacking of the planar units, extending through platinum to platinum bonds forming
349:
The synthesis and characterization of the platinum carbonyl dianions (n = 1–10), also known as Chini clusters or more correctly Chini-Longoni clusters, are recognized by the scientific community as the most spectacular result of Chini's work.
371:
148:
Binary carbonyl clusters consist only of metal and CO. They are the most widely studied and used metal carbonyl clusters. They arise in general by the condensation of unsaturated metal carbonyls. Dissociation of CO from
427:
Although the nuclearity of binary metal carbonyl clusters is usually six or fewer, carbido clusters often have higher nuclearities. Metal carbonyls of the iron and cobalt triads are well known to form
737:, Nelson, W. J. H., McPartlin, M., "The synthesis of the cluster dianion 2- by pyrolysis. X-Ray structure analysis of 2 and ", Journal of the Chemical Society, Dalton Transactions 1982, 2099.
802:
Jennifer C. Green, Malcolm L. H. Green, Gerard Parkin "The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds" Chem. Commun. 2012, 11481-11503.
459:
is used. Thus, 34 electrons in an organometallic complex predicts a dimetallic complex with a metal-metal bond. For higher nuclearity clusters, more elaborate rules are invoked including
370:
387:
is the most common member of this series of clusters. These clusters undergo reversible redox. They catalyze the hydrogenation of alkenes, ketones, and aldehydes.
391:
with redox properties act as a catalyst that helps transport sodium ions and electrons in the same direction across a liquid membrane, driven by pH-gradient. The
365:
subunits. Although these clusters were first reported in 1969 by Chatt and Booth, their structure were not established until Chini and
Longoni's work in 1976.
777:
Elena
Cariati, Claudia Dragonetti, Elena Lucenti, Dominique Roberto, "Tri- and Hexaruthnium Carbonyl Clusters" Inorganic Syntheses, 2004, Volume 35, 210.
464:
431:. Examples include and . Carbonyl carbides exist not only with fully encapsulated carbon (e.g., ) but also with exposed carbon centres as in Fe
506:
734:
786:
Ernestine W. Hill, John S. Bradley, "Tetrairon
Carbido Carbonyl Clusters" Inorganic Syntheses, 1990, Volume 27, Pages: 182–188.
72:
470:
Although clusters are often written with discrete M-M bonds, the nature of this bonding is unclear, especially when there are
329:
302:
225:
32:
chemistry, and many metal carbonyl clusters are in fact prepared from simple metal carbonyls. Simple examples include
824:
708:
Calabrese, J. C.; Dahl, L. F.; Chini, P.; Longoni, G.; Martinengo, S. J. Am. Chem. Soc., 1974, 96 (8), pp 2614–2616
361:
with strongly basic methanol under an atmosphere of CO. These clusters consist of stacks of triangularly shaped Pt
248:
117:, were reported starting in the 1930s, often by Walter Hieber. The structures were subsequently established by
55:
202:
44:
521:
Paul J. Dyson, J. Scott McIndoe "Transition Metal
Carbonyl Cluster Chemistry" Taylor & Francis, 2000.
558:
Hieber, W.; Lagally, H. (1943). "Über
Metallcarbonyle. XLV. Das Rhodium im System der Metallcarbonyle".
498:
428:
265:
118:
24:
is a compound that contains two or more metal atoms linked in part by metal–metal bonds and containing
455:
For low nuclearity clusters, bonding is often described as if it is localized. For this purpose, the
358:
33:
657:
185:
607:
502:
803:
787:
762:
738:
649:
615:
586:
567:
540:
490:
460:
456:
423:
The carbido cluster . The bent OsCO units are an artifact of the crystallographic analysis.
471:
25:
379:
29:
818:
661:
531:
Hieber, W.; Lagally, H. (1940). "Über
Metallcarbonyle. XXXV. Über Iridiumcarbonyl".
124:
791:
766:
653:
571:
544:
419:
17:
742:
619:
807:
28:(CO) as the exclusive or predominant ligand. The area is a subfield of
418:
638:"Paolo Chini: The Chemical Architect of Metal Carbonyl Clusters"
357:, 1 < n < 10. These clusters are prepared by reduction of
761:" Inorganic Syntheses, 1980, Volume 20, Pages: 212–215, 2007.
717:
Treguer, M.; Remita, H.; Pernot, P.; Khatouri, J.; Belloni,
636:
Paolieri, Matteo; Ciabatti, Iacopo; Fontani, Marco (2019).
637:
757:-Carbido-Nona-μ-Carbonyl-Hexacarbonylhexarhodate(2-) K
65:. High nuclearity clusters include and the stacked Pt
395:
platinum clusters, where n=4 – 6, are reduced by OH:
753:
S. Martinengo, D. Strumolo, P. Chini, "Dipotassium μ
560:Zeitschrift für Anorganische und Allgemeine Chemie
533:Zeitschrift für Anorganische und Allgemeine Chemie
691:
689:
353:Chini clusters follow the general formula of
8:
597:and its Identity with Previously Reported Rh
675:
673:
671:
465:polyhedral skeletal electron pair theory
167:
71:
631:
629:
482:
93:The first metal carbonyl clusters, Fe
7:
679:Bhaduri, S.; Sharma, K.; Mukesh, D.
733:Jackson, P. F., Johnson, B. F. G.,
14:
369:
144:Binary metal carbonyl clusters
1:
157:, which could trimerize to Ru
589:; Beck, Wolfgang (1963). "Rh
139:Classes of carbonyl clusters
841:
792:10.1002/9780470132586.ch36
767:10.1002/9780470132517.ch48
654:10.1007/s10876-019-01607-7
642:Journal of Cluster Science
699:, 2000, 78(11), 1318-1324
495:Chemistry of the Elements
493:; Earnshaw, Alan (1997).
572:10.1002/zaac.19432510110
545:10.1002/zaac.19402450311
681:Proc. Indian Acad. Sci.
69:triangules (n = 2–6).
424:
415:Metal carbido clusters
85:
22:metal carbonyl cluster
499:Butterworth-Heinemann
491:Greenwood, Norman N.
422:
119:X-ray crystallography
75:
743:10.1039/DT9820002099
719:J. J. Phys. Chem. A
620:10.1021/ja00891a040
429:carbido derivatives
359:hexachloroplatinate
808:10.1039/c2cc35304k
585:Corey, Eugene R.;
425:
380:trigonal prismatic
86:
825:Cluster chemistry
608:J. Am. Chem. Soc.
587:Dahl, Lawrence F.
508:978-0-08-037941-8
342:
341:
153:would give Ru(CO)
832:
810:
800:
794:
784:
778:
775:
769:
751:
745:
731:
725:
715:
709:
706:
700:
693:
684:
677:
666:
665:
648:(6): 1623–1631.
633:
624:
623:
614:(8): 1202–1203.
582:
576:
575:
555:
549:
548:
528:
522:
519:
513:
512:
497:(2nd ed.).
487:
472:bridging ligands
461:Jemmis mno rules
457:18-electron rule
373:
345:"Chini clusters"
168:
840:
839:
835:
834:
833:
831:
830:
829:
815:
814:
813:
801:
797:
785:
781:
776:
772:
760:
756:
752:
748:
732:
728:
716:
712:
707:
703:
697:Current Science
694:
687:
678:
669:
635:
634:
627:
604:
600:
596:
592:
584:
583:
579:
557:
556:
552:
530:
529:
525:
520:
516:
509:
489:
488:
484:
480:
453:
446:
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438:
434:
417:
410:
406:
402:
394:
386:
364:
356:
347:
337:
333:
326:
322:
310:
306:
299:
295:
284:
280:
273:
269:
256:
252:
245:
233:
229:
222:
210:
206:
200:
196:
189:
174:parent carbonyl
164:
160:
156:
152:
146:
141:
134:
130:
116:
112:
108:
104:
100:
96:
91:
83:
79:
76:Structure of Rh
68:
63:
59:
52:
48:
41:
37:
26:carbon monoxide
12:
11:
5:
838:
836:
828:
827:
817:
816:
812:
811:
795:
779:
770:
758:
754:
746:
726:
710:
701:
685:
683:1994, 713-716.
667:
625:
602:
598:
594:
590:
577:
550:
539:(3): 321–333.
523:
514:
507:
481:
479:
476:
452:
449:
444:
440:
436:
432:
416:
413:
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384:
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354:
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308:
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297:
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250:
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243:
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236:
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231:
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220:
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194:
191:
187:
183:
179:
178:
175:
172:
162:
158:
154:
150:
145:
142:
140:
137:
135:was obtained.
132:
128:
114:
110:
106:
102:
98:
94:
90:
87:
81:
77:
66:
61:
57:
50:
46:
39:
35:
30:metal carbonyl
13:
10:
9:
6:
4:
3:
2:
837:
826:
823:
822:
820:
809:
805:
799:
796:
793:
789:
783:
780:
774:
771:
768:
764:
750:
747:
744:
740:
736:
730:
727:
723:
720:
714:
711:
705:
702:
698:
692:
690:
686:
682:
676:
674:
672:
668:
663:
659:
655:
651:
647:
643:
639:
632:
630:
626:
621:
617:
613:
610:
609:
588:
581:
578:
573:
569:
566:(1): 96–113.
565:
561:
554:
551:
546:
542:
538:
534:
527:
524:
518:
515:
510:
504:
500:
496:
492:
486:
483:
477:
475:
473:
468:
466:
462:
458:
450:
448:
430:
421:
414:
403:+ 2OH ↔ n + H
398:
397:
396:
388:
383:The tetramer
381:
372:
368:
367:
366:
360:
351:
344:
338:
328:
318:
315:
314:
311:
301:
291:
288:
287:
276:
274:
264:
261:
260:
257:
247:
241:
238:
237:
234:
224:
218:
215:
214:
211:
192:
190:
184:
181:
180:
176:
173:
170:
169:
166:
143:
138:
136:
126:
122:
120:
88:
74:
70:
64:
53:
42:
31:
27:
23:
19:
798:
782:
773:
749:
729:
724:, 105, 6102.
721:
718:
713:
704:
696:
695:Bhaduri ,S.
680:
645:
641:
611:
606:
580:
563:
559:
553:
536:
532:
526:
517:
494:
485:
469:
454:
426:
389:
376:
352:
348:
147:
123:
92:
21:
15:
125:Paolo Chini
478:References
735:Lewis, J.
662:191176974
18:chemistry
819:Category
407:O + 1/2O
177:cluster
109:, and Rh
451:Bonding
89:History
660:
505:
439:and Fe
242:Os(CO)
219:Ru(CO)
186:Fe(CO)
149:Ru(CO)
54:, and
658:S2CID
443:C(CO)
435:C(CO)
399:(n-1)
171:metal
722:2001
601:(CO)
593:(CO)
503:ISBN
463:and
334:(CO)
323:(CO)
307:(CO)
296:(CO)
281:(CO)
270:(CO)
253:(CO)
230:(CO)
207:(CO)
197:(CO)
161:(CO)
131:(CO)
113:(CO)
105:(CO)
101:, Ir
97:(CO)
80:(CO)
60:(CO)
49:(CO)
38:(CO)
20:, a
804:doi
788:doi
763:doi
739:doi
650:doi
616:doi
605:".
568:doi
564:251
541:doi
537:245
393:n-1
16:In
821::
688:^
670:^
656:.
646:30
644:.
640:.
628:^
612:85
603:11
595:16
562:.
535:.
501:.
474:.
467:.
447:.
445:13
437:15
336:12
330:Ir
319:Ir
316:Ir
309:12
303:Rh
292:Rh
289:Rh
283:12
277:Co
266:Co
262:Co
255:12
249:Os
239:Os
232:12
226:Ru
216:Ru
209:12
203:Fe
201:,
193:Fe
182:Fe
163:12
133:12
121:.
115:16
107:12
99:12
82:12
62:10
56:Mn
51:12
45:Fe
43:,
34:Fe
806::
790::
765::
759:2
755:6
741::
664:.
652::
622:.
618::
599:4
591:6
574:.
570::
547:.
543::
511:.
441:4
433:5
409:2
405:2
401:n
385:4
363:3
355:n
332:4
325:8
321:2
305:4
298:8
294:2
279:4
272:8
268:2
251:3
244:5
228:3
221:5
205:3
199:9
195:2
188:5
159:3
155:4
151:5
129:3
111:6
103:4
95:3
84:.
78:4
67:3
58:2
47:3
40:9
36:2
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