Infected pancreatic necrosis: outcomes and clinical predictors of mortality. A post hoc analysis of the MANCTRA-1 international study

: The identification of high-risk patients in the early stages of infected pancreatic necrosis (IPN) is critical, because it could help the clinicians to adopt more effective management strategies. We conducted a post hoc analysis of the MANCTRA-1 international study to assess the association between clinical risk factors and mortality among adult patients with IPN. Univariable and multivariable logistic regression models were used to identify prognostic factors of mortality. We identified 247 consecutive patients with IPN hospitalised between January 2019 and December 2020. History of uncontrolled arterial hypertension (p = 0.032; 95% CI 1.135-15.882; aOR 4.245), qSOFA (p = 0.005; 95% CI 1.359-5.879; aOR 2.828), renal failure (p = 0.022; 95% CI 1.138-5.442; aOR 2.489), and haemodynamic failure (p = 0.018; 95% CI 1.184-5.978; aOR 2.661), were identified as independent predictors of mortality in IPN patients. Cholangitis (p = 0.003; 95% CI 1.598-9.930; aOR 3.983), abdominal compartment syndrome (p = 0.032; 95% CI 1.090-6.967; aOR 2.735), and gastrointestinal/intra-abdominal bleeding (p = 0.009; 95% CI 1.286-5.712; aOR 2.710) were independently associated with the risk of mortality. Upfront open surgical necrosectomy was strongly associated with the risk of mortality (p < 0.001; 95% CI 1.912-7.442; aOR 3.772), whereas endoscopic drainage of pancreatic necrosis (p = 0.018; 95% CI 0.138-0.834; aOR 0.339) and enteral nutrition (p = 0.003; 95% CI 0.143-0.716; aOR 0.320) were found as protective factors. Organ failure, acute cholangitis, and upfront open surgical necrosectomy were the most significant predictors of mortality. Our study confirmed that, even in a subgroup of particularly ill patients such as those with IPN, upfront open surgery should be avoided as much as possible. Study protocol registered in ClinicalTrials.Gov (I.D. Number NCT04747990)

Organic Amides as Suitable Precursors to Stabilize Stannylenes

This contribution demonstrates that deprotonated amides (amidates) can be used to stabilize stannylenes. Thus, the dimeric stannylene [Sn₂{μ-^<i>t</i>BuNC­(O)^<i>t</i>Bu}₂Cl₂] (<b>1</b>) was obtained by treating Li­{^<i>t</i>BuNC­(O)^<i>t</i>Bu} with 1 equiv of SnCl₂. Chloride exchange reactions of <b>1</b> with Li­{^<i>t</i>BuNC­(O)^<i>t</i>Bu} and Li­(HMDS) (HMDS = N­(SiMe₃)₂) lowered aggregation, affording the monomeric tetra- and tricoordinated tin­(II) derivatives [Sn­{^<i>t</i>BuNC­(O)^<i>t</i>Bu}₂] (<b>2</b>) and [Sn­{^<i>t</i>BuNC­(O)^<i>t</i>Bu}­(HMDS)] (<b>3</b>), respectively. Alternatively, <b>3</b> can be prepared by direct deprotonation of the amide with Sn­(HMDS)₂. Compounds <b>1</b>–<b>3</b> are stannylenes that contain an unprecedented SnNCO four-membered ring

Amidinatogermylene Complexes of Copper, Silver, and Gold

The synthesis of the first amidinatogermylene derivatives of the three coinage metals, including the first silver halide complex containing a germylene ligand of any type, has been achieved by reacting metal chloride precursors with the very bulky amidinatogermylene Ge­(^<i>t</i>Bu₂bzam)^<i>t</i>Bu (^<i>t</i>Bu₂bzam = <i>N</i>,<i>N</i>′-di­(<i>tert</i>-butyl)­benzamidinate). The reactions of Ge­(^<i>t</i>Bu₂bzam)^<i>t</i>Bu with an equimolar amount of MCl (M = Cu, Ag) led to the tetrameric complexes [M₄(μ₃-Cl)₄{Ge­(^<i>t</i>Bu₂bzam)^<i>t</i>Bu}₄] (M = Cu (<b>1</b>) and Ag (<b>2</b>)), which contain a pseudocubane-type M₄(μ₃-Cl)₄ core. A similar reaction with [AuCl­(tht)] (tht = tetrahydrothiophene) afforded the linear mononuclear derivative [AuCl­{Ge­(^<i>t</i>Bu₂bzam)^<i>t</i>Bu}] (<b>3</b>). The ionic digermylene derivatives [M­{Ge­(^<i>t</i>Bu₂bzam)^<i>t</i>Bu}₂]­[BF₄] (M = Cu (<b>4</b>) and Ag (<b>5</b>)) were satisfactorily prepared from the respective reactions of [Cu­(MeCN)₄]­[BF₄] and Ag­[BF₄] with two equivalents of Ge­(^<i>t</i>Bu₂bzam)^<i>t</i>Bu. The Ge-bound <i>tert</i>-butyl group of Ge­(^<i>t</i>Bu₂bzam)^<i>t</i>Bu plays an important role in stabilizing compounds <b>1</b>–<b>5</b> against hydrolysis, since, under similar reaction conditions, no pure complexes could be isolated from reactions of the same metal precursors with the chlorogermylene Ge­(^<i>t</i>Bu₂bzam)­Cl

Organic Amides as Suitable Precursors to Stabilize Stannylenes

This contribution demonstrates that deprotonated amides (amidates) can be used to stabilize stannylenes. Thus, the dimeric stannylene [Sn₂{μ-^<i>t</i>BuNC­(O)^<i>t</i>Bu}₂Cl₂] (<b>1</b>) was obtained by treating Li­{^<i>t</i>BuNC­(O)^<i>t</i>Bu} with 1 equiv of SnCl₂. Chloride exchange reactions of <b>1</b> with Li­{^<i>t</i>BuNC­(O)^<i>t</i>Bu} and Li­(HMDS) (HMDS = N­(SiMe₃)₂) lowered aggregation, affording the monomeric tetra- and tricoordinated tin­(II) derivatives [Sn­{^<i>t</i>BuNC­(O)^<i>t</i>Bu}₂] (<b>2</b>) and [Sn­{^<i>t</i>BuNC­(O)^<i>t</i>Bu}­(HMDS)] (<b>3</b>), respectively. Alternatively, <b>3</b> can be prepared by direct deprotonation of the amide with Sn­(HMDS)₂. Compounds <b>1</b>–<b>3</b> are stannylenes that contain an unprecedented SnNCO four-membered ring

Reaction of [Ru₃(CO)₁₂] with Phenazine: Synthesis of C-Metalated Derivatives That Formally Arise from a C–H Oxidative Addition or a Long-Distance C-to-N Prototropy

Three products, [Ru₃(μ-H)­(μ₃-{(C₆H₄)­(C₆H₃)­N₂})­(CO)₉] (<b>1</b>), [Ru₄(μ₄-{(C₆H₄)­(C₆H₃)­N₂H})­(μ-CO)­(CO)₁₀] (<b>2</b>), and [Ru₆(μ₅-{(C₆H₄)­(C₆H₃)­N₂H})­(μ-CO)₃(CO)₁₂] (<b>3</b>), have been prepared by treating [Ru₃(CO)₁₂] with phenazine. Compounds <b>2</b> and <b>3</b> are formed from compound <b>1</b> by stepwise addition of Ru­(CO)_<i>n</i> fragments. While compound <b>1</b> has a C-metalated ligand that arises from an oxidative addition of a phenazine C–H bond, compounds <b>2</b> and <b>3</b> contain a C-metalated phenazine NH tautomer. In these complexes, the resulting ligands are attached to three (<b>1</b>), four (<b>2</b>), or five (<b>3</b>) metal atoms using different coordination modes

Reaction of [Ru₃(CO)₁₂] with Phenazine: Synthesis of C-Metalated Derivatives That Formally Arise from a C–H Oxidative Addition or a Long-Distance C-to-N Prototropy

Three products, [Ru₃(μ-H)­(μ₃-{(C₆H₄)­(C₆H₃)­N₂})­(CO)₉] (<b>1</b>), [Ru₄(μ₄-{(C₆H₄)­(C₆H₃)­N₂H})­(μ-CO)­(CO)₁₀] (<b>2</b>), and [Ru₆(μ₅-{(C₆H₄)­(C₆H₃)­N₂H})­(μ-CO)₃(CO)₁₂] (<b>3</b>), have been prepared by treating [Ru₃(CO)₁₂] with phenazine. Compounds <b>2</b> and <b>3</b> are formed from compound <b>1</b> by stepwise addition of Ru­(CO)_<i>n</i> fragments. While compound <b>1</b> has a C-metalated ligand that arises from an oxidative addition of a phenazine C–H bond, compounds <b>2</b> and <b>3</b> contain a C-metalated phenazine NH tautomer. In these complexes, the resulting ligands are attached to three (<b>1</b>), four (<b>2</b>), or five (<b>3</b>) metal atoms using different coordination modes

Ruthenium Carbene Complexes Analogous to Grubbs‑I Catalysts Featuring Germylenes as Ancillary Ligands

Reactions of the first-generation Grubbs’ catalyst <i>trans</i>-[RuCl₂(CHPh)­(PCy₃)₂] (<b>1</b>) with the amidinatogermylenes Ge­(^<i>t</i>Bu₂bzam)­R (R = ^<i>t</i>Bu (<b>L</b>^<b>1</b>), CH₂SiMe₃ (<b>L</b>^<b>2</b>); ^<i>t</i>Bu₂bzam = <i>N</i>,<i>N</i>′-bis­(tertbutyl)­benzamidinate) have allowed the isolation and full characterization of the first specimens of Grubbs-type carbene complexes featuring heavier tetrylenes as ancillary ligands, namely, the disubstituted derivatives <i>trans-</i>[RuCl₂(CHPh)­(<b>L</b>^<b>1</b>)₂] (<b>3</b>) and <i>cis-</i>[RuCl₂(CHPh)­(<b>L</b>^<b>2</b>)₂] (<b>7</b>), which curiously differ in the arrangement of their germylene ligands. DFT calculations have revealed that the different volumes of <b>L</b>^<b>1</b> and <b>L</b>^<b>2</b> (the former is larger than the latter) are responsible for the different stereochemistry of <b>3</b> and <b>7</b>. NMR-monitoring of the reaction solutions has allowed the observation of the monosubstituted intermediates <i>trans</i>-[RuCl₂(CHPh)­(L)­(PCy₃)] (L = <b>L</b>^<b>1</b> (<b>2</b>), <b>L</b>^<b>2</b> (<b>5</b>)) and their evolution to either the disubstituted final product (for <b>L</b>^<b>1</b>) <i>trans</i>-[RuCl₂(CHPh)­(<b>L</b>^<b>1</b>)₂] (<b>3</b>) or the short-lived disubstituted intermediate (for <b>L</b>^<b>2</b>) <i>trans</i>-[RuCl₂(CHPh)­(<b>L</b>^<b>2</b>)₂] (<b>6</b>). Complex <b>7</b> arises from a <i>trans</i>-to-<i>cis</i> isomerization of intermediate <b>6</b>. As olefin metathesis catalysts, both <b>3</b> and <b>7</b> promoted the ring-closing metathesis of diethyl 2,2-diallylmalonate and the ring-opening metathesis polymerization of norbornene, but their catalytic activity decreased with the reaction time, indicating catalyst decomposition

Synthesis of Mixed Tin–Ruthenium and Tin–Germanium–Ruthenium Carbonyl Clusters from [Ru₃(CO)₁₂] and Diaminometalenes (M = Sn, Ge)

Diaminostannylenes react with [Ru₃(CO)₁₂] without cluster fragmentation to give carbonyl substitution products regardless of the steric demand of the diaminostannylene reagent. Thus, the Sn₃Ru₃ clusters [Ru₃{μ-Sn­(NCH₂^<i>t</i>Bu)₂C₆H₄}₃(CO)₉] (<b>4</b>) and [Ru₃{μ-Sn­(HMDS)₂}₃(CO)₉] (<b>6</b>) [HMDS = N­(SiMe₃)₂] have been prepared in good yields by treating [Ru₃(CO)₁₂] with an excess of the cyclic 1,3-bis­(<i>neo</i>-pentyl)-2-stannabenzimidazol-2-ylidene and the acyclic and bulkier Sn­(HMDS)₂, respectively, in toluene at 110 °C. The use of smaller amounts of Sn­(HMDS)₂ (Sn/Ru₃ ratio = 2.5) in toluene at 80 °C afforded the Sn₂Ru₃ derivative [Ru₃{μ-Sn­(HMDS)₂}₂(μ-CO)­(CO)₉] (<b>5</b>). Compounds <b>5</b> and <b>6</b> represent the first structurally characterized diaminostannylene-ruthenium complexes. While a further treatment of <b>5</b> with Ge­(HMDS)₂ led to a mixture of uncharacterized compounds, a similar treatment with the sterically alleviated diaminogermylene Ge­(NCH₂^<i>t</i>Bu)₂C₆H₄ provided [Ru₃{μ-Sn­(HMDS)₂}₂{μ-Ge­(NCH₂^<i>t</i>Bu)₂C₆H₄}­(CO)₉] (<b>7</b>), which is a unique example of Sn₂GeRu₃ cluster. All these reactions, coupled to a previous observation that [Ru₃(CO)₁₂] reacts with excess of Ge­(HMDS)₂ to give the mononuclear complex [Ru­{Ge­(HMDS)₂}₂(CO)₃] but triruthenium products with less bulky diaminogermylenes, indicate that, for reactions of [Ru₃(CO)₁₂] with diaminometalenes, both the volume of the diaminometalene and the size of its donor atom (Ge or Sn) are of key importance in determining the nuclearity of the final products

Synthesis of Mixed Tin–Ruthenium and Tin–Germanium–Ruthenium Carbonyl Clusters from [Ru₃(CO)₁₂] and Diaminometalenes (M = Sn, Ge)

Diaminostannylenes react with [Ru₃(CO)₁₂] without cluster fragmentation to give carbonyl substitution products regardless of the steric demand of the diaminostannylene reagent. Thus, the Sn₃Ru₃ clusters [Ru₃{μ-Sn­(NCH₂^<i>t</i>Bu)₂C₆H₄}₃(CO)₉] (<b>4</b>) and [Ru₃{μ-Sn­(HMDS)₂}₃(CO)₉] (<b>6</b>) [HMDS = N­(SiMe₃)₂] have been prepared in good yields by treating [Ru₃(CO)₁₂] with an excess of the cyclic 1,3-bis­(<i>neo</i>-pentyl)-2-stannabenzimidazol-2-ylidene and the acyclic and bulkier Sn­(HMDS)₂, respectively, in toluene at 110 °C. The use of smaller amounts of Sn­(HMDS)₂ (Sn/Ru₃ ratio = 2.5) in toluene at 80 °C afforded the Sn₂Ru₃ derivative [Ru₃{μ-Sn­(HMDS)₂}₂(μ-CO)­(CO)₉] (<b>5</b>). Compounds <b>5</b> and <b>6</b> represent the first structurally characterized diaminostannylene-ruthenium complexes. While a further treatment of <b>5</b> with Ge­(HMDS)₂ led to a mixture of uncharacterized compounds, a similar treatment with the sterically alleviated diaminogermylene Ge­(NCH₂^<i>t</i>Bu)₂C₆H₄ provided [Ru₃{μ-Sn­(HMDS)₂}₂{μ-Ge­(NCH₂^<i>t</i>Bu)₂C₆H₄}­(CO)₉] (<b>7</b>), which is a unique example of Sn₂GeRu₃ cluster. All these reactions, coupled to a previous observation that [Ru₃(CO)₁₂] reacts with excess of Ge­(HMDS)₂ to give the mononuclear complex [Ru­{Ge­(HMDS)₂}₂(CO)₃] but triruthenium products with less bulky diaminogermylenes, indicate that, for reactions of [Ru₃(CO)₁₂] with diaminometalenes, both the volume of the diaminometalene and the size of its donor atom (Ge or Sn) are of key importance in determining the nuclearity of the final products

Ruthenium Carbene Complexes Analogous to Grubbs‑I Catalysts Featuring Germylenes as Ancillary Ligands

Reactions of the first-generation Grubbs’ catalyst <i>trans</i>-[RuCl₂(CHPh)­(PCy₃)₂] (<b>1</b>) with the amidinatogermylenes Ge­(^<i>t</i>Bu₂bzam)­R (R = ^<i>t</i>Bu (<b>L</b>^<b>1</b>), CH₂SiMe₃ (<b>L</b>^<b>2</b>); ^<i>t</i>Bu₂bzam = <i>N</i>,<i>N</i>′-bis­(tertbutyl)­benzamidinate) have allowed the isolation and full characterization of the first specimens of Grubbs-type carbene complexes featuring heavier tetrylenes as ancillary ligands, namely, the disubstituted derivatives <i>trans-</i>[RuCl₂(CHPh)­(<b>L</b>^<b>1</b>)₂] (<b>3</b>) and <i>cis-</i>[RuCl₂(CHPh)­(<b>L</b>^<b>2</b>)₂] (<b>7</b>), which curiously differ in the arrangement of their germylene ligands. DFT calculations have revealed that the different volumes of <b>L</b>^<b>1</b> and <b>L</b>^<b>2</b> (the former is larger than the latter) are responsible for the different stereochemistry of <b>3</b> and <b>7</b>. NMR-monitoring of the reaction solutions has allowed the observation of the monosubstituted intermediates <i>trans</i>-[RuCl₂(CHPh)­(L)­(PCy₃)] (L = <b>L</b>^<b>1</b> (<b>2</b>), <b>L</b>^<b>2</b> (<b>5</b>)) and their evolution to either the disubstituted final product (for <b>L</b>^<b>1</b>) <i>trans</i>-[RuCl₂(CHPh)­(<b>L</b>^<b>1</b>)₂] (<b>3</b>) or the short-lived disubstituted intermediate (for <b>L</b>^<b>2</b>) <i>trans</i>-[RuCl₂(CHPh)­(<b>L</b>^<b>2</b>)₂] (<b>6</b>). Complex <b>7</b> arises from a <i>trans</i>-to-<i>cis</i> isomerization of intermediate <b>6</b>. As olefin metathesis catalysts, both <b>3</b> and <b>7</b> promoted the ring-closing metathesis of diethyl 2,2-diallylmalonate and the ring-opening metathesis polymerization of norbornene, but their catalytic activity decreased with the reaction time, indicating catalyst decomposition