Hydride complexes IrHCl(2)(PiPr(3))P(2) (1) and IrHCl(2)P(3) (2) [P = P(OEt)(3) and PPh(OEt)(2)] were prepared by allowing IrHCl(2)(PiPr(3))(2) to react with phosphite in refluxing benzene or toluene. Treatment of IrHCl(2)P(3), first with HBF(4).Et(2)O and then with an excess of ArCH(2)N(3), afforded benzyl azide complexes [IrCl(2)(eta(1)-N(3)CH(2)Ar)P(3)]BPh(4) (3, 4) [Ar = C(6)H(5), 4-CH(3)C(6)H(4); P = P(OEt)(3), PPh(OEt)(2)]. Azide complexes reacted in CH(2)Cl(2) solution, leading to the imine derivative [IrCl(2){eta(1)-NH=C(H)C(6)H(5)}P(3)]BPh(4) (5). The complexes were characterized by spectroscopy and X-ray crystal structure determination of [IrCl(2)(eta(1)-N(3)CH(2)C(6)H(5)){P(OEt)(3)}(3)]BPh(4) (3a) and [IrCl(2){eta(1)-NH=C(H)C(6)H(5)}{P(OEt)(3)}(3)]BPh(4) (5a). Both solid-state structure and (15)N NMR data indicate that the azide is coordinated through the substituted Ngamma [Ir]-Ngamma(CH(2)Ar)NNalpha nitrogen atom.

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The first example of evolution of an iridanaphthalene into an indanone through an intermediate indenyl is reported, serving as a good example of starting material to obtain indanones. Two new iridanaphthalenes are obtained by intramolecular C−H activation of a phenyl ring of a carbene ligand in [IrCp*{C(OMe)CHCPh 2 }(L)]PF 6 (L = PPh 2 Me, PMe 3 ) complexes. It is demonstrated that these iridanaphthalene complexes can undergo a thermal reaction to give indenyl complexes and 3-phenylindanone.M etallacyclic aromatic compounds incorporating transition metals are a subject of great interest, since they display a behavior that includes properties from both aromatic organic and organometallic compounds. Although many metallabenzenes of osmium, iridium, platinum, and ruthenium are known, to the best of our knowledge only two metallanaphthalenes have been reported, one with osmium 1 and another with iridium. 2 The importance of this type of metal-organic functionality is emphasized by the fact that metal cyclopentadienyls can be formed from transitory metallabenzenes. 3 Analogously, an osmanaphthalene has been proposed as intermediate leading to an indenyl complex. 4 Recently, we have reported that the new (methoxy)-alkenylcarbeneiridium complex [IrCp*Cl{C(OMe)CH CPh 2 }(PPh 2 Me)]PF 6 (1a) reacts with amines to undergo the unexpected cleavage of the O−CH 3 bond instead of the usual aminolysis. 5 This peculiar behavior has prompted us to further explore the reactivity of these types of compounds. Here, we report that treatment of [IrCp*Cl{C(OMe)CHCPh 2 }-(L)]PF 6 (L = PPh 2 Me (1a), PMe 3 (1b)) with AgPF 6 gives high yields of the iridanaphthalene complexes [IrCp*{C(OMe)-CHC(o-C 6 H 4 )(Ph)}(L)]PF 6 (L = PPh 2 Me (2a), PMe 3 (2b)) through an intramolecular C−H activation of one of the phenyl rings of the carbene ligand (eq 1).The structures of both iridanaphthalene complexes have been confirmed by single-crystal X-ray diffraction (see the Supporting Information). Figure 1 shows the complex cation 2a. The iridium atom becomes part of a metallanaphthalene moiety and the metal coordination sphere is completed with a pentamethylcyclopentadienyl (Cp*) and a phosphane ligand.The NMR spectra support the solid-state structures of 2a,b (see the Supporting Information).Remarkably, the iridanaphthalene moiety is not stable and refluxing 2 in 1,2-dichloroethane or toluene for 24 h gives 3-phenylindanone (4) (eq 2). The same transformation occurs also at longer reaction times in dichloromethane at 35°C (eq 2).

The trichlorostannyl complexes M(SnCl3)(CO)nP5-n (1−3: M = Mn, Re; P = PPh(OEt)2 (a), P(OEt)3 (b); n = 2, 3) were prepared by allowing chloro MCl(CO)nP5-n compounds to react with an excess of SnCl2·2H2O. Treatment of compounds 1−3 with NaBH4 in ethanol yielded the tin polyhydride derivatives M(SnH3)(CO)nP5-n (4−6). Treatment of 1−3 with MgBrMe gave the trimethylstannyl complexes M(SnMe3)(CO)nP5-n (7−9), and the reaction of 1−3 with MgBr(C≡CH) yielded the trialkynylstannyl derivatives M[Sn(C≡CH)3](CO)nP5-n (10, 11). The alkynylstannyl complexes M[Sn(C≡CR)3](CO)nP5-n (12−14: R = p-tolyl) were also prepared by allowing M(SnCl3)(CO)nP5-n compounds to react with Li+[C≡CR]- in thf. The complexes were characterized by spectroscopy and by X-ray crystal structure determinations of 4a, 6b, and 9b. Reaction of the tin trihydride complexes Re(SnH3)(CO)2P3 (6) with CO2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [Re{Sn[OC(H)=O]2(μ-OH)}(CO)2P3]2 (15). A reaction path for the formation of 15, involving the tin hydride bis(formate) intermediate Re[SnH{OC(H)=O}2](CO)2P3, is discussed. The X-ray crystal structure of 15b is reported

Triazenide [M(eta2-1,3-ArNNNAr)P4]BPh4 [M = Ru, Os; Ar = Ph, p-tolyl; P = P(OMe)3, P(OEt)3, PPh(OEt)2] complexes were prepared by allowing triflate [M(kappa2-OTf)P4]OTf species to react first with 1,3-ArN=NN(H)Ar triazene and then with an excess of triethylamine. Alternatively, ruthenium triazenide [Ru(eta2-1,3-ArNNNAr)P4]BPh4 derivatives were obtained by reacting hydride [RuH(eta2-H2)P4]+ and RuH(kappa1-OTf)P4 compounds with 1,3-diaryltriazene. The complexes were characterized by spectroscopy and X-ray crystallography of the [Ru(eta2-1,3-PhNNNPh){P(OEt)3}4]BPh4 derivative. Hydride triazene [OsH(eta1-1,3-ArN=NN(H)Ar)P4]BPh4 [P = P(OEt)3, PPh(OEt)2; Ar = Ph, p-tolyl] and [RuH{eta1-1,3-p-tolyl-N=NN(H)-p-tolyl}{PPh(OEt)2}4]BPh4 derivatives were prepared by allowing kappa1-triflate MH(kappa1-OTf)P4 to react with 1,3-diaryltriazene. The [Os(kappa1-OTf){eta1-1,3-PhN=NN(H)Ph}{P(OEt)3}4]BPh4 intermediate was also obtained. Variable-temperature NMR studies were carried out using 15N-labeled triazene complexes prepared from the 1,3-Ph15N=N15N(H)Ph ligand. Osmium dihydrogen [OsH(eta2-H2)P4]BPh4 complexes [P = P(OEt)3, PPh(OEt)2] react with 1,3-ArN=NN(H)Ar triazene to give the hydride-diazene [OsH(ArN=NH)P4]BPh4 derivatives. The X-ray crystal structure determination of the [OsH(PhN=NH){PPh(OEt)2}4]BPh4 complex is reported. A reaction path to explain the formation of the diazene complexes is also reported.

Keywords: Rhenium / Hydrido ligands / P ligands / Fluxionality; L = PPh n (OR) 3−n , n = 0−2, R = Me, Et] show them to be highly fluxional classical hydride complexes. In the case of the ethoxy compounds 5b, 5d and 5f, three hydride interchange processes were observed in the temperature range 283−173 K and their activation parameters were determined by NMR line-shape analysis. A mechanism is proposed for each. Protonation of 1 and 5 with HBF 4 ·OMe 2

Iridanaphthalene complexes are synthesized from the corresponding methoxy(alkenyl)carbeneiridium compounds. The electronic character of the substituents on the 6-position of the metallanaphthalene ring is crucial from the point of view of the stability of the iridanaphthalene, [Ir[upper bond 1 start]Cp*{=C(OMe)CH=C(o-C[upper bond 1 end]6H4)(Ph)}(PMe3)]PF6, vs. its transformation to the corresponding indanone derivatives. Stability studies of the iridanaphthalene compounds revealed that strong electron donor substituents (-OMe) stabilize the iridanaphthalene, while weak electron donor (-Me) and electron withdrawing (-NO2) groups favor the formation of indanone derivatives. Two possible indanone isomers can be obtained in the conversion of the unstable iridanaphthalene complexes and a mechanism for the formation of these isomers is proposed.

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