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Tetracationic cyclo-tetraphosphane [(L C ) 4 P 4 ] 4+ as triflate salt ( 3 [OTf] 4 ) (L C = 4,5-dimethyl-1,3-diisopropyl-imidazol-2-yl) is obtained in high yield from the reduction of [L C PCl 2 ] + ( 4 [OTf]) with 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine ( 6 ) and represents the first salt of the cationic cyclo-phosphane series with the general formula [L  n  P  n  ]  n + . Theoretical calculations reveal the electrophilic nature of the P atoms within the P 4 -ring due to the influence of the imidazoliumyl-substituents. Further reduction of 3 [OTf] 4 with 6 affords the unexpected formation of the notricyclane P 7 -type cation [(L C ) 3 P 7 ] 3+ ( 9 [OTf] 3 ). Selective transition metal mediated [2 + 2]-fragmentation of 3  4+ is achieved when 3 [OTf] 4 is reacted with Fe 2 (CO) 9 , Pd(PPh 3 ) 4 and Pt(PPh 3 ) 4 leading to the formation of the dicationic diphosphene complexes [(η 2 -L C P[double bond, length as m-dash]PL C )Fe(CO) 4 ] 2+ ( 12 [OTf] 2 ) and [(η 2 -L C P[double bond, length as m-dash]PL C )M(PPh 3 ) 2 ] 2+ ( 13 [OTf] 2 for M = Pd; 14 [OTf] 2 for M = Pt). In contrast, the reaction of 3 [OTf] 4 with an excess of AuCl(tht) gives rise to the formation of the five-membered ring complex [((L C ) 4 P 4 )AuCl 2 ] 3+ ( 15 [OTf] 3 ), where the Au(i) atom reductively inserts into a P-P bond of 3  4+ .

chemical science

Formation of an imidazoliumyl-substituted [(LC)4P4]4+tetracation and transition metal mediated fragmentation and insertion reaction (LC= NHC)