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Illusions that create a sense of ownership over a virtual body have been widely used to investigate the characteristics of our bodily experience. Despite the great potential of 360-degree videos to implement full-body ownership illusion, research is in its early stages, and no validated tools—neither commercial nor free—are available for the scientific and clinical community. In the current study, we present and discuss the development and feasibility results of a free 360-degree video-based body ownership illusion that researchers and scholars can experience using a cardboard headset with their smartphones. Forty-six participants underwent the 360-degree video-based full-body ownership illusion, visualizing in a first-person perspective (1PP) or in a mirror view the pre-recorded body of a young female performer. All participants were exposed to a congruent visuo-tactile condition (embodiment condition) and to an incongruent visuo-tactile condition (control condition). Participants completed the Embodiment Questionnaire and the Objectified Body Consciousness (OBC) scale. Results revealed that in the congruent visuo-tactile condition (compared to the control one), participants experienced a strong illusion in terms of body ownership, self-location, and agency. In terms of visual perspective, there was no difference in embodiment feelings between participants who experienced the illusion in 1PP and those who underwent a mirror perspective. Lastly, the control beliefs subscale (i.e., OBC scale) displayed a positive correlation with the self-location illusion susceptibility. Overall, these results point to the feasibility of this novel tool as immersive 360-degree video-based scenarios to deliver bodily illusions, and they open new avenues for future clinical interventions.

Objective The general objective of the current study was to investigate the efficacy of a novel self-help virtual therapeutic experience (specifically, the COVID Feel Good intervention) in lowering the psychological burden experienced during the COVID-19 lockdowns in four European countries. Methods We focused on participants recruited from June 2020 to May 2021 in the context of a European multicenter project including four university/academic sites. The total number of participants in the longitudinal studies was 107 (study 1, N = 40; study 2, N = 29; study 3, N = 38). The randomized controlled trial (study 4) included 31 participants in total, 16 in the intervention group and 15 in the control group. Primary outcome measures were depression, anxiety, stress symptoms, perceived stress level, and perceived hopelessness. The secondary outcome was experienced social connectedness. Results Using separate linear mixed-effects models, the most consistent result across countries was a reduction in perceived stress after the participation in the COVID Feel Good intervention. By pooling the results of the models using a random-effects meta-analysis, we found that after the COVID Feel Good intervention, participants reported a decrease in perceived general distress (mean standardized effect size for general distress in the treatment groups compared with the control conditions was -0.52 [p =.008, 95% confidence interval = -0.89 to -0.14]) and an increase in the perceived social connection (mean standardized effect size for social connection using COVID Feel Good compared with the control conditions was 0.50 [p ≤.001, 95% confidence interval = 0.25 to 0.76]). Conclusions Findings of this study indicate that a virtual self-help intervention is effective in reducing psychological distress. These results contribute to the growing literature supporting the use of digital psychological therapies to relieve psychological distress among the general population during the COVID-19 pan

Despite advances in our understanding of the behavioral and molecular factors that underlie the onset and maintenance of Eating Disorders (EDs), it is still necessary to optimize treatment strategies and establish their efficacy. In this context, over the past 25 years, Virtual Reality (VR) has provided creative treatments for a variety of ED symptoms, including body dissatisfaction, craving, and negative emotions. Recently, different researchers suggested that EDs may reflect a broader impairment in multisensory body integration, and a particular VR technique—VR body swapping—has been used to repair it, but with limited clinical results. In this paper, we use the results of a systematic review employing PRISMA guidelines that explore inner body perception in EDs (21 studies included), with the ultimate goal to analyze the features of multisensory impairment associated with this clinical condition and provide possible solutions. Deficits in interoception, proprioception, and vestibular signals were observed across Anorexia and Bulimia Nervosa, suggesting that: (a) alteration of inner body perception might be a crucial feature of EDs, even if further research is needed and; (b) VR, to be effective with these patients, has to simulate/modify both the external and the internal body. Following this outcome, we introduce a new therapeutic approach—Regenerative Virtual Therapy—that integrates VR with different technologies and clinical strategies to regenerate a faulty bodily experience by stimulating the multisensory brain mechanisms and promoting self-regenerative processes within the brain itself.

Oncological treatments are responsible for many of the physical changes (aesthetic and functional) associated with cancer. Because of this, cancer patients are at high risk of developing mental health problems. The aim of this study is to propose an innovative Virtual Reality (VR) training that uses a somatic technique (i.e., embodiment) to create a bridge with the bodily dimension of cancer. After undergoing a psycho-educational procedure, a combination of exposure, out-of-body experience, and body swapping will gradually train the patient to cope with cancer-related difficulties, increasing stress tolerance, and patient empowerment. The most engaging step of this advanced form of Stress Inoculation Training is the body swapping experience, which will guide the patient in embodying a resilient cancer patient who is facing similar difficulties. Through the VR ability to simulate the human brain functioning, and the potential of embodiment to hook to the somatic dimension of illness, we expect that once the concepts endured through the patient’s experience of resilience are triggered, the patient will be more prone to implement functional coping strategies in real life, reaching empowerment and adjusting to the post-treatment difficulties. When the scenarios are built and the training tested, our intervention could be used to support patients with different oncological diseases and who are treated in different cancer hospitals, as well as patients with other non-oncological problems (e.g., social anxiety). Future research should focus on using our paradigm for other clinical populations, and supporting cancer patients in coping with different distressing situations.

Despite noticeable advances, we are still far from a real understanding of AN, especially concerning how patients experience their bodies. In light of its aforementioned relevance in this pathology, we suggest a deeper investigation of this aspect by combining insights from different research fields (i.e., clinical practice and neuropsychology) and technological advances. With that in mind, the goal of the BODY-FRIEND project is to use BS to study body experience in AN from a psychological and physiological point of view. It will do this by using state-of-the-art technologies, such as VR-based FBI and physiological sensors, to learn more about the role of the frame of reference (first- or third-person perspective) and the virtual body parameters (in terms of BMI). Once these mechanisms have been better understood, it might be possible to investigate the effects of repeated BS exposure on relevant AN clinical body-related symptoms as body distortion. These data might also be used to develop machine learning models to identify the main factors implicated in the pathology and thus determine what might be the most successful intervention targets. This project will be carried out in collaboration with the Istituto Auxologico Italiano IRCCS (Italy) and the Humane Technology Lab from the Catholic University of Sacred Heart (Italy).

Break in presence (BIP) is a concept that refers to that condition in which the person immersed in a virtual reality ( VR) environment disengages from it, due to various factors, and focuses more on the real environment. BIP occurs due to certain factors that may be related to errors in the sensory data of the virtual reality environment (VRE). These errors can influence the multisensory integration process by generating a multisensory conflict, which results in BIP phenomena. Several studies have identified a correlation between BIP and the physiological (e. g., electrocardiogram/ ECG) responses of people, showing that there is a correlation between these two aspects. In this study, we used the physiological (ECG) data collected in a previous study, in which participants were involved in a Full Body illusion (FBI) experiment, i. e. a paradigm that uses VR to generate a synchronous multisensory stimulation condition and an asynchronous multisensory stimulation condition. The FBI asynchronous stimulation condition can generate a multisensory conflict that is the same phenomenon underlying BIP. In this study, we used these physiological (ECG) data, collected throughout the FBI, to train different machine learning (ML) models to be able to detect the multisensory conflict underlying BIP from ECG tracings alone. The results showed that two ML models, Decision Tree and Random Forest, are able to detect the multisensory conflicts underlying BIP.

Affective computing is a rapidly growing field that aims to understand human emotions through Artificial Intelligence. One of the most promising ways to achieve this goal is the use of physiological data (e.g. electrocardiogram-ECG) and Machine Learning (ML) algorithms to classify affective states. ECG correlates, such as Heart Rate Variability (HRV) and its features, are reported as viable indicators in both dimensional approaches, especially for valence, and in detecting discrete emotions. In this preliminary study, we used the ECG data from the open-source HCI Tagging Database, which includes physiological data and self-referred feedback from 30 subjects who watched videos designed to elicit different emotions. The subjects evaluated their reactions using a three-dimensional affective space defined by arousal, valence, and dominance levels and reported the emotions they felt. To classify the affective states, we trained and tested different classification algorithms on the HRV features, using as labels, each self-reported feedback (i.e., valence, arousal, dominance, and emotions). The results showed that HRV features, when combined with normalization methods and ML algorithms, were effective in recognizing emotions as experienced by individuals. In particular, the study showed that Decision Tree was the best-performing algorithm for predicting emotions based on HRV data. Additionally, an Explainable AI (XAI) model provided insights into the weight of these features in the ML discrimination phases. Overall, the study highlights the potential of HRV as a valid and unobtrusive source for detecting emotional states.

To explore the potential of VR in improving cancer patients' well-being, the Humane Technology Lab from the Catholic University of Sacred Heart (Italy) has developed the 360-VIRTOncology Project. This project will be carried out in collaboration with the Radiotherapy Unit of Veneto Institute of Oncology (IOV) from Padua (Italy), which will support the data collection for the project.

Despite advances in our understanding of the behavioral and molecular factors that underlie the onset and maintenance of Eating Disorders (EDs), it is still necessary to optimize treatment strategies and establish their efficacy. In this context, over the past 25 years, Virtual Reality (VR) has provided creative treatments for a variety of ED symptoms, including body dissatisfaction, craving, and negative emotions. Recently, different researchers suggested that EDs may reflect a broader impairment in multisensory body integration, and a particular VR technique—VR body swapping—has been used to repair it, but with limited clinical results. In this paper, we use the results of a systematic review employing PRISMA guidelines that explore inner body perception in EDs (21 studies included), with the ultimate goal to analyze the features of multisensory impairment associated with this clinical condition and provide possible solutions. Deficits in interoception, proprioception, and vestibular signals were observed across Anorexia and Bulimia Nervosa, suggesting that: (a) alteration of inner body perception might be a crucial feature of EDs, even if further research is needed and; (b) VR, to be effective with these patients, has to simulate/modify both the external and the internal body. Following this outcome, we introduce a new therapeutic approach—Regenerative Virtual Therapy—that integrates VR with different technologies and clinical strategies to regenerate a faulty bodily experience by stimulating the multisensory brain mechanisms and promoting self-regenerative processes within the brain itself.

The Metaverse can be defined as a hybrid (digital/physical) environment offering places for rich user interaction. In this view, the main feature of the Metaverse is a twofold link between the virtual and physical worlds: (a) behavior in the physical world influences the experience in the virtual one and, (b) behavior in the virtual world influences the experience in the real one. Furthermore, any change in the physical world is mirrored in its digital representation (the digital twin), and feedback is sent in the opposite direction (i.e., if the avatar is touched, haptic feedback is provided to the physical body). Currently, this is achieved through 3D shared XR worlds, biosensors and activity sensors (from the real to the virtual world), two-way Internet of Things (IoT) object connections, social media, and wearable devices including smartphones (from the virtual world to the real one). Our view is that bridging technologies that simulate both the external world and the internal world (our bodily experience) will allow the simulated, cognitive, and embodied dimension of the Metaverse to merge, thereby transforming it into the ultimate clinical technology. In particular, it will allow for the emergence of Regenerative VR: the integration of external and internal simulated technologies to rewrite a faulty bodily experience and to regenerate the wellbeing of an individual.

The Metaverse can be defined as a hybrid (digital/physical) environment offering places for rich user interaction. In this view, the main feature of the Metaverse is a twofold link between the virtual and physical worlds: (a) behavior in the physical world influences the experience in the virtual one and, (b) behavior in the virtual world influences the experience in the real one. Furthermore, any change in the physical world is mirrored in its digital representation (the digital twin), and feedback is sent in the opposite direction (i.e., if the avatar is touched, haptic feedback is provided to the physical body). Currently, this is achieved through 3D shared XR worlds, biosensors and activity sensors (from the real to the virtual world), two-way Internet of Things (IoT) object connections, social media, and wearable devices including smartphones (from the virtual world to the real one). Our view is that bridging technologies that simulate both the external world and the internal world (our bodily experience) will allow the simulated, cognitive, and embodied dimension of the Metaverse to merge, thereby transforming it into the ultimate clinical technology. In particular, it will allow for the emergence of Regenerative VR: the integration of external and internal simulated technologies to rewrite a faulty bodily experience and to regenerate the wellbeing of an individual.

The anionic clusters [Fe5MN(CO)14Cp]2- [M = Mo (1) or W (2)] were synthesized from [Fe4N(CO)12]- and [MCp(CO)3]- in refluxing acetonitrile. The clusters [Fe3M3N(CO)18]3- [M = Mo (3) orW(4)] were prepared by reaction of [Fe4N(CO)12]- with [M2(CO)10]2- under the same conditions. The molybdenum- containing anions 1 and 3 are obtained in higher yields than 2 and 4. The reaction of the tetranuclear iron cluster with [Mo(ç6-Me3C6H3)(CO)3] affords a mixture of [Fe3Mo3N(CO)18]3- and [HFe5MoN(CO)16]2- (5). The solid state structures of the clusters 1, 2 and 3 have been determined; they consist of six metal atoms, arranged in octahedral metal cages encapsulating a ì6-N ligand. The cyclo- Introduction The interest in heterometallic clusters is still growing, and several examples of their application in catalysis can be found in the literature.[1] In homogeneous catalysis, mixed metal species are preferred, due to the presence of polar metal2metal bonds which can tune electron density at the metal centres, thus modifying the reactivity of the coordinated ligands.[2] In the field of heterogeneous catalysis, mixed-metal species can be exploited for the formation of bimetallic particles which are extraordinarily uniform in their morphology and composition.[3] In this context, the stability of the cage due to the interstitial atoms can avoid [a] Dipartimento di Scienze dell’ Ambiente e del Territorio, Universita` di Milano-Bicocca Piazza della Scienza 1, 20126 Milano, Italy rpergola@mailserver.unimi.it Fax: (internat.) 1 39-02/236-2748 [b] Dipartimento di Chimica Inorganica, Metallorganica ed Analitica and Centro del CNR Universita` di Milano, via G. Venezian 21, 20133 Milano, Italy [c] Dipartimento di Biologia Strutturale e Funzionale, Universita` degli studi dell’Insubria, via J. H. Dunant 3, 21100 Varese, Italy [d] Dipartimento di Chimica Strutturale e Stereochimica Inorganica and Centro del CNR 2 Universita` di Milano via G. Venezian 21, 20133 Milano, Italy E-mail: m.manasser

The cluster [Ir4(CO)11(CPh CHPh)] was obtained by reaction of [HIr4(CO)11] and diphenylacetylene by refluxing in tetrahydrofuran (THF), with yields approaching 80%. The solid state structure was determined on the [NEt4] salt; the cluster possesses a tetrahedral metallic framework, with three edge bridging carbonyls. The vinyl fragment, having two phenyl rings in cis, is bound in axial position and donates only one electron to the cluster, since the C C double bond (1.34 A, ) does not interact with any iridium atom. The 13C-NMR of the cluster, recorded at 90°C, allows full assignment of the signals. The cluster [Ir6(CO)14(COOMe)2]2- was obtained by nucleophilic attack of MeONa on [Ir6(CO)16], in anhydrous methanol at room temperature. The solid state structure was determined on its [N(PPh3)2] salt. Two methoxycarbonyl fragments are on adjacent metal vertices of the octahedral framework.

The compound [Felr3(CO)12]- can be obtained by degradation of [Felr4(C0)l5]2- under a carbon monoxide atmosphere as well as by reduction of an equimolar mixture of [Fe(CO)5] and [Ir4(CO)12] in alcoholic NaOH under 1 atm of carbon monoxide. The molecular structure of the anion consists of a tetrahedron of metal atoms surrounded by twelve carbonyl groups: nine are terminally bound whereas three are bridging the edges of the Felr2 basal face. The dianion [Fe2lr2(C0)l2]2- was obtained by several different ways, the most selective being the condensation of [Fe2(CO)9] with [Ir(CO)4]-. The molecular structure of the dianion is based on a tetrahedral cluster of metal atoms and consists of an apical Ir(CO)3 group co-ordinated by three metal-metal bonds to a basal Fe2lr(CO)9 fragment containing two Fe(CO)2 units and one Ir(CO)2 group linked to each other by a metal-metal bond and bridging carbonyl groups.The salt [PPh4]2[Fe2lr2(CO)12] reacts with [Au(PPh3)CI] to give [PPh4][Fe2lr2(CO)12{m3-Au(PPh3)}]. The metal framework of the anion is a trigonal bipyramid with the Au(PPh3) moiety in one of the apical positions, the other being occupied by a Fe(CO)3 group. Each edge of the equatorial triangle, formed by one iron and two iridium atoms, is spanned by a bridging carbonyl ligand, and two terminal CO groups are attached to each metal of this triangle.

The two clusters [HFe5NiN(CO)14]2- (1) and [HFe4Ni2N(CO)13]2- (2) were obtained by reaction of [Fe4N(CO)12]- and [Ni6(CO)12]2- in refluxing MeCN and EtCN, respectively, along with other Fe-Ni mixed metal clusters. Their solid state structures were determined on the [PPh4]+ salts, and both have an octahedral metal cage, containing an interstitial nitrogen atom. The two Ni atoms in 2 are cis, with a Ni-Ni separation of 2.724(1) Å. The two anions have different stereochemistry of the carbonyl ligands: in 1, five CO's are semi-bridging, and the remaining nine are terminal; in 2 there are three asymmetric bridging and ten terminal ligands (two for each iron and one for each nickel). The hydride ligands were located in the final difference maps, both bridging a Ni-Fe edge of the clusters but, thanks to the better quality of the diffraction data, the metal-hydrogen distances were refined only in 2. In this cluster, the Fe-H and Ni-H bond lengths are 1.77(2) and 1.79(2) Å, respectively. © 2006 Elsevier B.V. All rights reserved.

The reaction between norbornene (C7H10) and Ir-6(CO)(16) in refluxing toluene yields the substituted cluster [Ir-6(CO)(14)(C7H8)]. In the solid state, the six iridium atoms define an octahedral metal cage, and one face is capped by the C7H8 ligand, coordinated through a 1,2-vinylidene unit. The loss of two hydrogen atoms from the olefin is, presumably, the result of a double oxidative addition of its C-H bonds, followed by elimination of a hydrogen molecule from the cluster. The bonding parameters of the organic fragment, as well as the architecture of the carbonyl ligands, closely match those found in the alkyne-substituted [Ir-6(CO)(14)(PhCCPh)] complex. The cluster [Ir-6(CO)(14)(C7H8)] was characterized through H-1-, C-13- and bidimensional COSY NMR.

The three clusters [Fe6Ni6N2 (CO)24]n- (n = 2-4) have been isolated, and their solid-state structures determined. The clusters are composed by three face-sharing octahedra, with the external ones filled by two interstitial nitride. The addition of electrons brings about swelling of the central, empty octahedron. Cyclic voltammetry shows that redox conversions of the three clusters are totally reversible. Extended Hückel and density functional calculations have been performed, to explain this behavior. © 2005 Académie des sciences. Published by Elsevier SAS. All rights reserved.

The dianionic cluster [Co5MoN(CO)(14)](2-) (1) was synthesized from [Co6N(CO)(15)](-) and [Mo-2(CO)(10)](2-) in refluxing acetonitrile. The solid-state structure of the [Ph4P](+) salt was determined. It consists of an octahedral metal cage, enclosing a six-coordinate nitrido ligand. Typical bond lengths are: Co-N 1.88 Angstrom, Mo-N 2.03 Angstrom, Co-Co 2.61 Angstrom and Co-Mo 2.84 Angstrom showing that there is very little, if any, preferential interaction of the interstitial atom with that of molybdenum. The cluster reacts with Au(PPh3)Cl in THF at room temperature forming the derivative [Co5MoN(CO)(14){AuPPh3}](-) (2). The gold atom caps an MoCO2 face of the octahedron, with short Au-Co (2.68 Angstrom) and long Au-Mo (3.16 Angstrom) bonds, showing that both metal atoms are necessary for coordination, but Au-I binds better with the cobalt atoms. Electrochemical studies have pointed out that cluster 1 has good redox capabilities in that it is able to support reversibly the progressive addition of three electrons. EPR measurements on the corresponding trianion confirm. the lack of preferential interaction between the Mo site and the interstitial nitride atom. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

The cluster [Rh11(CO)14(C7H7)3] (1) was obtained from the reaction of [Rh6(CO)16] and an excess of cycloheptatriene in refluxing toluene. Initially, the substituted cluster [Rh6(CO)13(C7H8)] (2) could be identified spectroscopically, which is transformed into 1 after prolonged refluxing. In the solid state, the eleven rhodium atoms define a trioctahedral metal cage, condensed through a common edge. The three planar, equivalent C7 rings sit on the top of triangular faces. The spectroscopic characterisation of the product is hampered by its low solubility.

The carbonyl hydride cluster Ir4H8(CO)(4)(PPh3)(4) (1) has been formed in hig(31)P NMR spectra, two isomeric forms (1A and 1B) of the cluster are present in CD2Cl2 solution at room temperature, and they do not interconvert in the explored temperature range. However, if a solid sample of the cluster is dissolved at 188 K, only 1A is detected by NMR spectroscopy. The structure of 1B could be proposed on the basis of the T-1 relaxation times of the various hydrides: it results by localised exchange of H and CO around two vertices of the tetrahedral frame.h yield and purity by heating a mixture of Ir-4(CO)(12) and PPh3 in toluene at 90 degreesC under hydrogen at atmospheric pressure. The product has been characterised by microanalysis, spectroscopy (IR, H-1 and P-31 NMR) and X-ray diffraction. In the solid state one hydrogen, one CO and one triphenylphosphane ligand are terminally bonded to each iridium atom, whereas four hydride ligands are bridging. All the hydrogen atoms were directly located by X-ray analysis at an average H-Ir distance of 1.55 Angstrom. (for the terminal H) and 1.75 Angstrom (for the p-H). As shown by H-1 and P-31 NMR spectra, two isomeric forms (1A and 1B) of the cluster are present in CD2Cl2 solution at room temperature, and they do not interconvert in the explored temperature range. However, if a solid sample of the cluster is dissolved at 188 K, only 1A is detected by NMR spectroscopy. The structure of 1B could be proposed on the basis of the T-1 relaxation times of the various hydrides: it results by localised exchange of H and CO around two vertices of the tetrahedral frame

The cluster [FeNi5(CO)(13)] (2-) (1) was obtained by reaction of Fe(CO)(5) and [Ni-6(CO)(12)](2-) (2), in acetonitrile at room temperature. Its solid state structure was determined on the [NEt4]() salt, and consists of a trigonally distorted octahedron, with six edge-bridging ligands. This assembly strictly recalls the architecture of the prototypical [Ni-6(CO)(12)](2-) anion, by formal replacement of one Ni(CO) unit with the Fe(CO)(2) fragment. However, the requirements of the additional ligand have sterical consequences on the other carbonyl groups, which can not be coplanar as in the all-nickel cluster. [FeNi5(CO)(13)](2-) reacts readily with acids, to yield the already known [HFe3Ni(CO)(12)](-) (3), and with CO, being stepwise fragmented to species of lower nuclearity, ending with [Fe3Ni(CO)(12)](2-) (4) or [Fe-2(CO)(8)](2-). The solid state structure of the tetranuclear [Fe3Ni(CO)(12)](2-) was also determined, and is reported here. (C) 2002 Elsevier Science B.V. All rights reserved.

The cluster [Ir-6(CO)(13)(C7H8)] (1) was synthesized from [Ir-6(CO)(16)] and excess cycloheptatriene in refluxing toluene. In the solid state, the six iridium atoms define an octahedral metal cage, and one face is capped by the mu(3)-eta(2):eta(2):eta(2)-C7H8 ligand, which is a six-electrondonor, through the three C C double bonds. Reaction of 1 with Na2CO3 in THF yields [Ir-6(CO)(12)(C7H7)](-) (2). In this octahedral anion, the cycloheptatrienyl ring is almost planar and is coordinated to a triangular face in the mu(3)-eta(2):eta(3):eta(2)-C7H8 fashion. Reaction of 1 or 2 with NaOH in THF yields [Ir-6(CO)(12)(C7H8)(2-) (3), in which a mu(3)-eta(3):eta(3):eta(3)-C7H8 is also present. The H-1 NMR spectra of 1 and 3 show five signals, which were assigned to the nonequivalent hydrogen atoms by bidimensional experiments. The spectrum of 2 shows a singlet, even at low temperature, in agreement with a highly fluxional ligand. The interconversions of 1 to the anions 2 and 3, respectively, have been followed by electrochemical investigations. The neutral [Ir-6(CO)(13)(C7H8)] proves to undergo a two-electron reduction, which, being accompanied by decarbonylation, affords the dianion [Ir-6(CO)(12)(C7H8)](2-). In turn, the latter undergoes a two-electron oxidation, which followed by deprotonation affords the monoanion [Ir-6(CO)(12)(C7H7)](-)

The cluster [HIr5(CO)(12)](2-) (1) was prepared by condensation of [HIr4(CO)(11)](-) and [Ir(CO)(4)](-) (molar ratio 1:1) in refluxing THF, with almost quantitative yields. Its solid state structure was determined by X-ray diffraction at low temperature on the salt [PPh3CH2Ph](2)[HIr5(CO)(12)]. The metal atoms define a trigonal bipyramidal arrangement. The hydride ligand was located indirectly as a bridge between apical and equatorial metal atoms. The phosphine-substituted cluster [HIr4(CO)(10)PPh3](-) (2) was synthetized by CO displacement on [HIr4(CO)(11)], in THF at room temperature. This reaction is selective, with no traces of polysubstitution products. In the solid state, the hydride and the triphenylphosphine are axially bound on basal iridium atoms; the terminal hydrogen atom was directly located by X-ray analysis at a Ir-H distance of 1.57(9) Angstrom. On the contrary, two isomers are present in THF solution, and they interconvert tepidly at room temperature, as shown by H-1 and P-31 NMR spectra

The cluster [Fe5MnN(CO)16]2 (1) was synthesized from [Fe6N(CO)15]3- and Mn2(CO)10, in refluxing EtCN, or [Fe4N(CO)12]- and [FeMn(CO)9] -. Its solid state structure was determined on the [Me3NCH2Ph] + salt, and consists of an octahedral metal cage, enclosing a six-coordinated nitrido ligand. The position of the manganese atom in the solid state could be established, despite some crystallographic disorder, by considering the local stereochemistry of the ligands. The cluster [Fe6N(CO)14NO]2- (2) was obtained in moderate yields by the reaction of [Fe4N(CO12] with Mo(CO)3(EtCN)3. The nitrosyl is formed by oxidation of the starting nitride, and the source of the oxygen is presumably a carbonyl, whose splitting is mediated by the molybdenum complex. This process is the first example of an oxidation of a nitride in a carbonyl cluster. The solid state structure of the iron cluster is also octahedral, and the linear nitrosyl ligand was unambiguously located from the short Fe–N bond distance, and from dishomogeneous distribution of ligands. Cyclic voltammetric studies have shown that electron transfer processes are followed by chemical reactions thus testifying that no stable redox congeners exist for these two nitride clusters.